ES2905258T3 - Method for filling a mixed refrigerant containing 2,3,3,3-tetrafluoropropene - Google Patents

Abstract

A method for filling a refrigerant mixture composed of difluoromethane (HFC-32) and 2,3,3,3-tetrafluoropropene (HFO-1234yf), HFC-32 being present in the liquid phase in an amount of 10-90% by weight based on 100% by weight of total HFC-32 and HFO-1234yf, comprising the method, when transferring the refrigerant mixture in a liquid state to a target vessel or equipment from a feed vessel, adjust, immediately prior to transfer, the proportion (initial composition) of HFC-32 in the liquid phase of the refrigerant mixture in the feed vessel a (x + y1) % by weight (minimum value) a (x + a) % by weight (maximum value), so that the proportion of HFC-32 in the liquid phase of the refrigerant mixture in the feed vessel falls within a range of ±a % by weight of a target composition (x) of HFC-32 during the start and end of the transfer, where ±a is a set tolerance (a >= 0); x is an objective composition with the condition that 10 <= x <= 90, which excludes an interval satisfying y1 > a; and y1 is a lower limit of a difference between the target composition and the initial composition, and is represented by Equation (1): **(See formula)** where L1 = 0.0002a + 0.016, M1 = 0.072a + 3.4761, N1 = 7.914a + 187.52 and P1 = 1194.8a - 9.58.

Description

DESCRIPTION

Method for filling a mixed refrigerant containing 2,3,3,3-tetrafluoropropene

technical field

The present invention relates to a method for filling a refrigerant mixture comprising 2,3,3,3-tetrafluoropropene.

Background art

Recently, the revision of refrigerants is making progress in the fields of refrigeration and air conditioning from the point of view of preventing global warming. In the field of automotive air conditioners, refrigerants with a global warming potential (GWP) of 150 or more are regulated by the European Union (EU) Fluorinated Gases Regulation. Next, 2,3,3,3-tetrafluoropropene (HFO-1234yf, CF3CF=CH2) having a GWP of 4 has been used.

As for fixed-type refrigeration and air conditioning systems, currently used refrigerants such as R-410A (GWP: 2,088), R-404A (GWP: 3,922), R-407C (Gw P: 1,770) and 1,1,1,2-tetrafluoroethane (hereinafter HFC-134a) (GWP: 1,430), have a high GWP and therefore are being regulated in developed countries from the point of view of not only reducing the CO ² , but also reduce HFCs (hydrofluorocarbons or fluorinated hydrocarbons). The development of alternative refrigerants is an urgent issue. Refrigerants should be selected among various refrigerants, considering the application, operating conditions, and other conditions, from multiple points of view, including environmental friendliness, safety, performance, and economic efficiency. Various types of refrigerants are currently being proposed, along with fluorocarbons and natural refrigerants; however, no refrigerant currently satisfies all requirements, including flammability, efficiency, and GWP value. It is necessary to select the correct coolant for the correct location, which depends on the application, operating conditions, and other conditions.

Among refrigerants, HFO-1234yf refrigerants have attracted attention due to their low GWP and low toxicity in fields other than the field of automobile air conditioners. HFO-1234yf refrigerants are an important candidate for an alternative to HFC-134a refrigerants in the field of large refrigeration and air conditioning systems. However, as alternatives to R-410A and other refrigerants for use in, for example, fixed-type refrigeration and air conditioning systems, HFO refrigerants by themselves have a low vapor pressure and raise concerns about insufficient capacity or performance degradation, compared to conventional coolants. Also, HFO refrigerants are known to be slightly flammable.

Accordingly, non-azeotropic refrigerant blends of various refrigerants have recently been proposed to improve performance and achieve non-flammability (JP-A-2010-47754, JP-A-2011-525204 and JP-A-2011-522947) .

However, many of the HFC and HFO-1234yf blends are non-azeotropic blends and therefore undergo compositional changes during phase changes, such as evaporation and condensation. This is because low-boiling components are more likely to evaporate, and high-boiling components are more likely to condense. This tendency is noticeable in the case of evaporation, that is, a phase change from liquid to vapor, and is particularly noticeable when the components of the mixture have a large difference in their boiling points. For this reason, when such a non-azeotropic mixture is transferred from one container to another container, the mixture is normally removed from the liquid phase so as not to induce phase changes.

However, a mixture of components that have a large difference in boiling points experiences a compositional change of a few percent, even when the mixture is withdrawn from the liquid phase. This is because the reduction in pressure and the increase in gas phase space due to extraction of the mixture lead to the evaporation of low boiling components in the liquid phase. A composition change of a few percent not only causes a significant change in refrigerant performance to reduce capacity and efficiency, but also has a major impact on refrigerant safety such as flammability (JP-A -10-197108 and JP-B-3186065).

In particular, difluoromethane (HFC-32, CH ² F ² ), which is likely to be used as a refrigerant blend with HFO-1234yf, has a very high refrigeration capacity; however, the difference in boiling point between HFC-32 and HFO-1234yf is at least 20 K. The compositional changes that occur during the transfer of such a refrigerant mixture from a feed vessel (for example, a gas cylinder or a tank truck) to a refrigeration and air conditioning system or other tanks are of a not insignificant level in terms of performance. Furthermore, not only in terms of performance, but also quality assurance of the coolant mixture, it is important to control composition changes within the established tolerance of the coolant mixture.

For example, when a refrigerant mixture comprising HFO-1234yf and HFC-32 is transferred at 40°C, without taking no measurement, up to 3-4 wt% difference in composition from target composition occurs when all liquid is removed prior to transfer. In this case, the composition change rate is approximately ±4% by weight of the target composition, and the expected cooling capacity and cooling capacity (e.g. coefficient of performance (COP)) of the composition cannot be guaranteed. objective. Therefore, it is important to control the rate of composition change within as narrow a range as possible. In addition, the composition changes vary significantly depending on the type and composition ratio of the non-azeotropic refrigerant, and it is difficult to predict the range of composition changes without actual measurement. Summary of the invention

technical problem

A primary object of the present invention is to provide a method for filling a refrigerant mixture that allows composition changes of a non-azeotropic refrigerant mixture composed of 2,3,3,3-tetrafluoropropene and difluoromethane during transfer of the mixture to fall into an acceptable range of coolant performance.

Solution to the problem

The present inventors conducted extensive research on methods of filling a liquefied gas in order to solve the problem of composition changes occurring in a non-azeotropic mixture comprising two liquefied gases having different boiling points when the mixture is stored in a hermetically sealed container and transferred from the liquid phase to another container.

Specifically, the present invention provides a method for filling a non-azeotropic refrigerant mixture composed of difluoromethane and 2,3,3,3-tetrafluoropropene.

Therefore, the present invention provides a method for filling a refrigerant mixture composed of difluoromethane (HFC-32) and 2,3,3,3-tetrafluoropropene (HFO-1234yf), with HFC-32 being present in the liquid phase in a amount of 10-90% by weight based on 100% by weight of the total of HFC-32 and HFO-1234yf, comprising the method, by transferring the refrigerant mixture in a liquid state to a target vessel or equipment from a feed vessel,

adjust, immediately before transfer, the proportion (initial composition) of HFC-32 in the liquid phase of the refrigerant mixture in the feed vessel to (xy ¹ ) % by weight (minimum value) to (xa) % by weight (maximum value), so that the proportion of HFC-32 in the liquid phase of the refrigerant mixture in the feed container falls within a range of ±a % by weight of a target composition (x) of HFC-32 during the transfer start and end, where

±a is a set tolerance (a > 0);

X is an objective composition with the condition that 10 < x < 90, which excludes an interval that satisfies y ¹ >a; ey ¹ is a lower bound on a difference between the target composition and the initial composition, and is represented by Equation (1):

1000 ^{yi = L ix} 3 ^{- M ix} 2 ^{+ N xx - P i (} 1 ^{) ,}

where L1 = ^0.0002a 0.016,

M1 = 0.072a ^3.4761 ,

N1 = 7.914a ^187.52 and

P1 = ^1194.8a - 9.58.

Also, the present invention provides a method for filling a refrigerant mixture composed of difluoromethane (HFC-32) and 2,3,3,3-tetrafluoropropene (HFO-1234yf), e1HFC-32 being present in the liquid phase in an amount of 10-90% by weight based on 100% by weight of the total of HFC-32 and HFO-1234yf, comprising the method, by transferring the refrigerant mixture in a liquid state to a target vessel or equipment from a feed vessel that is filled with the coolant mixture in an amount of < 70% by weight of the maximum fill quantity of the coolant mixture,

adjust, immediately before transfer, the proportion (initial composition) of HFC-32 in the liquid phase of the refrigerant mixture in the feed vessel to (xy ² ) % by weight (minimum value) to (xa) % by weight (maximum value), so that the proportion of HFC-32 in the liquid phase of the refrigerant mixture in the feed container falls within a range of ±a % by weight of a target composition (x) of HFC-32 during the start and finish of the transfer, where

±a is a set tolerance (a > 0);

x is an objective composition with the condition that 10 < x < 90, which excludes an interval that satisfies y ² >a; ey ² is a lower bound on a difference between the target composition and the initial composition, and is represented by Equation (6):

1000y2 = L2x3 - M2x2 N2x - P2 (6 ),

where L ² = -0.0016 to 0.0169,

M2 = ^-0.1765 to 3.4316,

^N2 = -1.87 to 180.08 and

P2 = ^1119.5 to 148.9.

In addition, the present invention provides a method for filling a refrigerant mixture composed of difluoromethane (HFC-32) and 2,3,3,3-tetrafluoropropene (HFO-1234yf), e1HFC-32 being present in the liquid phase in an amount of 10-90% by weight based on 100% by weight of the total of HFC-32 and HFO-1234yf, comprising the method, by transferring the refrigerant mixture in a liquid state to a target vessel or equipment from a feed vessel,

adjust, immediately before transfer, the proportion (initial composition) of HFC-32 in the liquid phase of the refrigerant mixture in the feed vessel to (xy ³ ) % by weight (minimum value) to (xa) % by weight (maximum value), so that the proportion of HFC-32 in the liquid phase of the refrigerant mixture in the feed container falls within a range of ±a % by weight of a target composition (x) of HFC-32 during the transfer start and end, where

±a is a set tolerance (a > 0);

x is an objective composition with the condition that 10 < x < 90, which excludes an interval satisfying y3 > a; and y3 is a lower bound on a difference between the target composition and the initial composition, and is represented by Equation (11):

1000y3 = L3x3 - M3 ^x 2 N3 ^x - P3 (11 ),

where L3 = ^0.0003a 0.0172,

M3 = 0.0962a ^3.6851 ,

N3 = ^9.704a 196.9, and

^P3 = 1241.2a - 93.54.

Furthermore, the present invention provides a method for filling a refrigerant mixture composed of difluoromethane (HFC-32) and 2,3,3,3-tetrafluoropropene (HFO-1234yf), HFC-32 being present in the liquid phase in an amount of 10-90% by weight based on 100% by weight of the total of HFC-32 and HFO-1234yf, comprising the method, by transferring the refrigerant mixture in a liquid state to a target vessel or equipment from a feed vessel,

adjust, immediately before transfer, the proportion (initial composition) of difluoromethane in the liquid phase of the refrigerant mixture in the feed vessel to (x y4) % by weight (minimum value) to (x 2.0) % by weight ( maximum value), so that the proportion of the difluoromethane in the liquid phase of the refrigerant mixture in the feed vessel falls within a range of ±2.0% by weight of a target composition (x) of the difluoromethane during the start and end of the transfer, where

b is an amount (% by weight) initially filled in the feed container;

x is a target composition with the condition that 10 < x < 90, which excludes an interval satisfying y4 > 2; and y4 is a lower bound on a difference between the target composition and the initial composition, and is represented by Equation (16):

1000y4 = L4x3 - M4x2 N4x - P4 (16 ),

where u = 0.0001 b 0.0081,

M4 = ^0.0195b 1.958,

N4 = 0.9878b 118.91, and

P4 = -0.176b 2408.7.

Furthermore, the present invention provides a method for filling a refrigerant mixture composed of difluoromethane (HFC-32) and 2,3,3,3-tetrafluoropropene (HFO-1234yf), HFC-32 being present in the liquid phase in an amount of 10-90 wt% based on 100 wt% of total HFC-32 and HFO-1234yf,

the method comprising, by transferring the refrigerant mixture in a liquid state to a target container or equipment from a feed container,

adjust, immediately before transfer, the proportion (initial composition) of the difluoromethane in the liquid phase of the refrigerant mixture in the feed vessel to (x y5) % by weight (minimum value) to (x 1.5) % by weight ( maximum value), so that the proportion of the difluoromethane in the liquid phase of the refrigerant mixture in the feed vessel falls within a range of ±1.5% by weight of a target composition (x) of the difluoromethane during the start and end of the transfer, where

b is an amount (% by weight) initially filled in the feed container;

x is an objective composition with the condition that 10 < x < 90, which excludes an interval that satisfies y5 > 1.5; and y5 is a lower bound on a difference between the target composition and the initial composition, and is represented by Equation (22):

1 0 0 0 and 5 = L 5 ^x 3 - M 5 ^x 2 + N 5 ^x - P 5 ( 2 2 ) ,

where L5 = ^0.00005b 0.0092,

M5 = 0.0171b ^2.1013 ,

N5 = 0.8528b ^125.11 , and

P5 = ^-2.372b 1972.3.

In addition, the present invention also provides a method for filling a refrigerant mixture composed of difluoromethane (HFC-32) and 2,3,3,3-tetrafluoropropene (HFO-1234yf), e1HFC-32 being present in the liquid phase in an amount 10-18.5% by weight or 60-90% by weight based on 100% by weight of the total of HFC-32 and HFO-1234yf, comprising the method, when transferring the refrigerant mixture in a liquid state to a target container or equipment from a feeding container,

adjust, immediately before transfer, the proportion (initial composition) of difluoromethane in the liquid phase of the refrigerant mixture in the feed vessel to (x y6) % by weight (minimum value) to (x 1.0) % by weight ( maximum value), so that the proportion of the difluoromethane in the liquid phase of the refrigerant mixture in the feed vessel falls within a range of ±1.0% by weight of a target composition (x) of the difluoromethane during the start and end of the transfer, where

b is an amount (% by weight) initially filled in the feed container;

x is a target composition with the proviso that 10 < x < 18.5 wt% or 60 < x < 90 wt%, excluding a range satisfying y6 > 1.0; and

y6 is a lower bound on a difference between the target composition and the initial composition, and is represented by Equation (28):

1000y6 = L¿x3 - M¿x2 N6X - Pg (28) ,

where L6 = 0.00009b 0.0086,

M6 = 0.0183b 2.003,

N6 = 0.9237b 117.29, and

P6 = -1.055b 1292.7.

Preferred embodiments of the invention are as defined in the attached dependent claims and/or in the following detailed description.

The method of the present invention for filling a non-azeotropic refrigerant mixture composed of difluoromethane (HFC-32, CH ² F ² ) and 2,3,3,3-tetrafluoropropene (HFO-1234yf, CF3CF =CH2).

The present method has the characteristic that, when transferring a refrigerant mixture of HFC-32/HFO-1234yf, which is a non-azeotropic refrigerant and has a composition of 10-90% by weight of HFC-32 in the liquid phase, to a target vessel or equipment from a feed vessel, the proportion of HFC-32 in the liquid phase of the refrigerant mixture in the feed vessel is adjusted before transfer to a specified range.

[1] Filling method for each filling quantity

The mix ratio is described below in terms of a coolant mix before it is transferred to a target vessel or equipment from a feed container that is filled with the coolant mix in an amount < 100 wt% or 70 wt%. of a maximum filling quantity of the refrigerant mixture.

The term "maximum fill quantity" (100% by weight of the maximum fill quantity) used in this specification refers to a maximum quantity that can be filled in a container, as defined in international legislation regarding the transport or in Japan's High Pressure Gas Safety Legislation. According to Japan's High Pressure Gas Safety Legislation, the maximum filling quantity is calculated as follows:

- G = V/C

- G: Mass (kg) of fluorocarbon

- V: Capacity (L) of the container

- C: Constant depending on the type of fluorocarbon

The filling constant C is determined here in Japan as a value obtained by dividing 1.05 by the specific gravity of the gas at 48°C. When it comes to export, according to international law, the filling constant C is defined as a value obtained by dividing 1.05 by the specific gravity of the gas at 65 °C when passing through tropical regions, and is defined as a value obtained by dividing 1.05 by the specific gravity of the gas at 45 °C when only non-tropical regions are involved.

In the transfer of an HFC-32/HFO-1234yf refrigerant mixture to a target vessel or equipment from a feed vessel, a smaller amount of the mixture than was initially filled into the feed vessel results in a smaller change in temperature. composition of HFC-32 in the liquid phase of the refrigerant mixture in the feed vessel during the start and finish of the transfer.

The maximum fill amounts calculated using the fill constants are shown below in decreasing order:

A maximum fill amount calculated using a value obtained by dividing 1.05 by the specific gravity of the gas at 45°C as the fill constant > a maximum fill amount calculated using a value obtained by dividing 1.05 by the specific gravity of the gas at 48°C as the fill constant > a maximum fill quantity calculated using a value obtained by dividing 1.05 by the specific gravity of the gas at 65 °C as the fill constant.

A value obtained by dividing 1.05 by the specific gravity of the gas at 45°C or 65°C is then used as the fill constant.

(1) Filling method in which a refrigerant mixture is filled into a container in an amount < the amount calculated using a value obtained by dividing 1.05 by the specific gravity of the gas at 65 °C as the filling constant The mixture ratio is described below in terms of a refrigerant mixture before it is transferred to a target vessel or equipment from a feed vessel that is filled with the refrigerant mixture in an amount < the maximum filling amount (100% by weight) of the mixture refrigerant, the maximum filling amount is calculated using a value obtained by dividing 1.05 by the specific gravity of the gas at 65°C as the filling constant. (1-1) Filling method that allows the composition of HFC-32 to fall within a range of ±a % by weight of the target composition (x) of HFC-32

An inventive gas transfer filling method for filling a refrigerant mixture composed of HFC-32 and HFO-1234yf such that HFC-32 is present in the liquid phase in an amount of 10-90% by weight based on into 100% by weight of total HFC-32 and HFO-1234yf, the method of transferring the refrigerant mixture in a liquid state to a target vessel or equipment from a feed vessel that is filled with the refrigerant mixture in a quantity < 100% by weight of the maximum filling quantity of the coolant mixture, has the following feature. Specifically, the proportion (initial composition) of HFC-32 in the liquid phase of the refrigerant mixture in the feed vessel is adjusted immediately before transfer to axy ¹ wt% (minimum value) axa wt% (maximum value), for the proportion of HFC-32 in the liquid phase of the refrigerant mixture in the feed vessel to fall within a set tolerance (±a wt%) of a target composition (x) of HFC-32 during start-up and completion of the transfer.

±a: tolerance setting (a > 0)

x: target composition (with the condition that 10 < x < 90, which excludes an interval that satisfies an inequality: yi > a)

and ¹ : a lower bound of a difference between the target composition and the initial composition, and ¹ which is represented by Equation (1) below:

1000yi = Lix3 - Mix2 NiX - PL(1)

L1 = ^0.0002a 0.016

M1 = 0.072a ^3.4761

N1 = 7.914a ^187.52

P1 = ^1194.8a - 9.58.

The "±a" (established tolerance) is a difference between a reference value (a target composition (x) of HFC-32) and a maximum or minimum acceptable value of the reference value. Specifically, "±a" is an acceptable difference relative to the target composition.

According to the present method, the proportion of HFC-32 in the liquid phase of the mixture in a feed vessel is adjusted, before transfer, to a specific range; therefore, even when the feed vessel is filled with the cooling mixture in an amount of 100% by weight of the maximum filling amount of the cooling mixture, changes in composition in a target vessel or equipment fall within a acceptable range, ie, ±a wt% of the target composition, until transfer is complete.

The HFC-32 "target composition" is the concentration of HFC-32 in the overall composition (liquid phase and vapor phase) of the HFC-32/HFO-1234yf refrigerant mixture, and is calculated in a target vessel or equipment .

The boiling point of HFC-32 is lower than that of HFO-1234yf. Therefore, when the space created due to refrigerant removal is filled with vapor evaporated from the liquid phase during transfer, e1HFC-32 evaporates in a greater amount than that of HFO-1234yf, causing a reduction in the concentration of HFC-32 in the liquid phase. For this reason, HFC-32 is preferably filled into a feed container before transfer in an amount greater than that of the target composition. The a value above is usually set to 0.5 < a < 3.0.

An example is described below with respect to a method that performs transfer at a handling temperature of 40°C. For example, according to Japan's High Pressure Gas Safety Legislation, it is prohibited to handle a container at a temperature of >40°C; therefore, particularly in Japan, the handling temperature is 0-40°C when transferring. Also in international legislation, it is required to avoid handling high pressure gas at a high temperature. A higher temperature during the transfer (at the time of handling) causes a larger compositional change associated with the transfer. Therefore, the conditions for transfer at a handling temperature of 40°C can be applied to the conditions for transfer at a handling temperature of 0-40°C.

(1-2) Filling method that allows the composition of HFC-32 to fall within a range of ±2.5% by weight of the target composition (x) of HFC-32

Next, an embodiment is described in which the set tolerance (±a) is ±2.5.

In an embodiment of the present method for filling a refrigerant mixture composed of HFC-32 and HFO-1234yf such that HFC-32 is present in the liquid phase in an amount of 10-90% by weight based on 100% by weight of the total of HFC-32 and HFO-1234yf, when transferring the refrigerant mixture in a liquid state to a target vessel or equipment from a feed vessel, the proportion (initial composition) of HFC-32 in the liquid phase of the refrigerant mixture in the feed vessel is preferably adjusted, before transfer, to x yA % by weight to x 2.5 % by weight, so that the proportion of HFC-32 in the liquid phase of the refrigerant mixture in the feed vessel falls from a range of ±2.5% by weight of a target composition (x) of HFC-32 during the start and finish of the transfer.

(In the above, x is a target composition, provided that 10 < x <90; and yA is a lower bound on a difference between the target composition and the initial composition, and is represented by Equation (2): 1000yA = 0.0166X3 - 3.6757x2 20 8.97x - 3006.3 (2) . )

In this embodiment, referring to Equation (2) above, when transferring the refrigerant mixture of HFC-32/HFO-1234yf to a target vessel or equipment from a feed vessel, the proportion of HFC-32 in the liquid phase of the coolant mixture in the feed vessel is adjusted, prior to transfer, to about x - 1.9 wt% to x 2.5 wt%. Changes in composition in a target container or equipment may thus fall within the acceptable range of ±2.5% by weight of the target composition until transfer is complete.

The boiling point of HFC-32 is lower than that of HFO-1234yf. Therefore, when the space created due to refrigerant removal is filled with vapor evaporated from the liquid phase during transfer, e1HFC-32 evaporates in a greater amount than that of HFO-1234yf, causing a reduction in the concentration of HFC-32 in the liquid phase. For this reason, HFC-32 is preferably filled into a feed container before transfer in an amount greater than that of the target composition. In the method for filling a refrigerant mixture in which the HFC-32 composition in the HFC-32/HFO-1234yf refrigerant mixture is made to fall within the acceptable range of ±2.5% by weight of the target composition in a container or target equipment until transfer is complete, the upper limit of the HFC-32 composition in the liquid phase of the HFC-32/HFO-1234yf refrigerant mixture immediately prior to transfer is 2.5% by weight of the target composition of HFC-32.

Also, when the mixture contains HFC-32 in an amount of 90% by weight, changes in the composition of HFC-32 are small; therefore, even when the initial composition of HFC-32 is approximately -1.9% by weight of the target composition (90% by weight), the proportion of HFC-32 in the liquid phase of the mixture falls within ±2.5% by weight of the target composition until the transfer is complete.

(1-3) Filling method that allows the composition of HFC-32 to fall within a range of ±2.0% by weight of the target composition (x) of HFC-32

Next, an embodiment is described in which the set tolerance (±a) is ±2.0.

In one embodiment of a method of the present invention for filling a refrigerant mixture composed of HFC-32 and HFO-1234yf such that HFC-32 is present in the liquid phase in an amount of 10-90% by weight based on 100 % by weight of total HFC-32 and HFO-1234yf, when transferring the refrigerant mixture in a liquid state to a target vessel or equipment from a feed vessel, the proportion (initial composition) of HFC-32 in the liquid phase of the refrigerant mixture in the feed vessel is preferably adjusted, before transfer, at x yB wt% to x 2.0 wt%, so that the proportion of HFC-32 in the liquid phase of the refrigerant mixture in the feed vessel falls within a range of ±2.0% by weight of the target composition (x) of HFC-32 during the start and finish of the transfer.

(In the above, x is a target composition, provided that 10 < x < 90; and yB is a lower bound on a difference between the target composition and the initial composition, and is represented by Equation (3):

1000yB = 0.0162X3 - 3.5639x2 2 00. 6x - 2347 .6 (3) . )

In this embodiment, referring to Equation (3) above, when transferring the refrigerant mixture of HFC-32/HFO-1234yf to a target vessel or equipment from a feed vessel, the proportion of HFC-32 in the liquid phase of the coolant mixture in the feed vessel is adjusted, prior to transfer, to about x - 1.4 wt% to x 2.0 wt%. Changes in composition in a target container or equipment may thus fall within the acceptable range of ±2.0% by weight of the target composition until transfer is complete.

For the same reason as described above, HFC-32 is preferably filled into a feed container before transfer in an amount greater than that of the target composition. In the method for filling a refrigerant mixture, in which the HFC-32 composition in the HFC-32/HFO-1234yf refrigerant mixture is made to fall within the acceptable range of ±2.0% by weight of the target composition in a container or target equipment until transfer is complete, the upper limit of the HFC-32 composition in the liquid phase of the HFC-32/HFO-1234yf refrigerant blend immediately prior to transfer is 2.0% by weight of the target composition of HFC-32.

Also, when the mixture contains HFC-32 in an amount of 90% by weight, changes in the composition of HFC-32 are small; therefore, even when the initial composition of HFC-32 is approximately -1.4% by weight of the target composition (90% by weight), the proportion of HFC-32 in the liquid phase of the mixture falls within ±2.0% by weight of the target composition until the transfer is complete.

(1-4) Filling method that allows the composition of HFC-32 to fall within a range of ±1.5% by weight of the target composition (x) of HFC-32

Next, an embodiment is described in which the set tolerance (±a) is ±1.5.

In an embodiment of a method of the present invention for filling a refrigerant mixture composed of HFC-32 and HFO-1234yf in such a way that HFC-32 is present in the liquid phase in an amount of 10-32% by weight or 42 90 % by weight based on 100% by weight of the total of HFC-32 and HFO-1234yf, when transferring the refrigerant mixture in a liquid state to a target vessel or equipment from a feed vessel, the proportion (initial composition) of HFC- 32 in the liquid phase of the refrigerant mixture in the feed vessel is preferably adjusted, before transfer, at x yC % by weight to x 1.5 % by weight, so that the proportion of HFC-32 in the liquid phase of the refrigerant mixture in the feed vessel falls within ±1.5% of the target composition (x) of HFC-32 during the start and finish of the transfer. When a = 1.5 and 32 < x < 42, then yC > a; therefore, x is within a range of 10-32 wt% or 42-90 wt%.

(In the above, x is a target composition; and yC is a lower bound on a difference between the target composition and the initial composition, and is represented by Equation (4):

1000yc = 0.0169X3 - 3.6374x2 199.88x - 1760.3 (4) . )

In this embodiment, referring to Equation (4) above, when transferring the refrigerant mixture of HFC-32/HFO-1234yf to a target vessel or equipment from a feed vessel, the proportion of HFC-32 in the liquid phase of the coolant mixture in the feed vessel is adjusted, prior to transfer, to about x - 0.9 wt% to x 1.5 wt%. Changes in composition in a target container or equipment may thus fall within the acceptable range of ±1.5% by weight of the target composition until transfer is complete.

For the same reason as described above, HFC-32 is preferably filled into a feed container before transfer in an amount greater than that of the target composition. In the method for filling a refrigerant mixture, in which the HFC-32 composition in the HFC-32/HFO-1234yf refrigerant mixture is made to fall within the acceptable range of ±1.5% by weight of the target composition in a container or target equipment until transfer is complete, the upper limit of the HFC-32 composition in the liquid phase of the HFC-32/HFO-1234yf refrigerant mixture immediately prior to transfer is 1.5% by weight of the target composition of HFC-32.

Also, when the mixture contains HFC-32 in an amount of 90% by weight, changes in the composition of HFC-32 are small; therefore, even when the initial composition of HFC-32 is approximately -0.9% by weight of the target composition (90% by weight), the proportion of HFC-32 in the liquid phase of the mixture falls within ±1.5% by weight of the target composition until the transfer is complete.

(1-5) Filling method that allows the composition of HFC-32 to fall within a range of ±1.0% by weight of the target composition (x) of HFC-32

Next, an embodiment is described in which the set tolerance (±a) is ±1.0.

In an embodiment of a method of the present invention for filling a refrigerant mixture composed of HFC-32 and HFO-1234yf such that HFC-32 is present in the liquid phase in an amount of 10-14% by weight or 65% -90% by weight based on 100% by weight of the total of HFC-32 and HFO-1234yf, when transferring the refrigerant mixture in a liquid state to a target vessel or equipment from a feed vessel, the proportion (initial composition) of HFC-32 in the liquid phase of the refrigerant mixture in the feed vessel is preferably adjusted, before transfer, at x yD wt% to x 1.0 wt%, so that the proportion of HFC-32 in the liquid phase of the refrigerant mixture in the feed vessel is within a range of ±1.0% by weight of the target composition (x) of HFC-32 during the start and finish of the transfer. When a = 1.0, and 14 < x < 65, then yD > a; therefore, x is within a range of 10-14 wt% or 65-90 wt%. (In the above, x is as defined above; and yd is a lower bound on a difference between the target composition and the initial composition, and is represented by Equation (5):

1000yD = 0.0160X3 - 3.5312x2 19 6.02x - 1210.8 (5) . )

In this embodiment, referring to Equation (5) above, when transferring the refrigerant mixture of HFC-32/HFO-1234yf to a target vessel or equipment from a feed vessel, the proportion of HFC-32 in the liquid phase of the coolant mixture in the feed vessel is adjusted, prior to transfer, to about x - 0.5 wt% to x 1.0 wt%. Changes in composition in a target container or equipment may thus fall within the acceptable range of ±1.0% by weight of the target composition until transfer is complete.

For the same reason as described above, HFC-32 is preferably filled into a feed container before transfer in an amount greater than that of the target composition. In the method for filling a refrigerant mixture, in which the HFC-32 composition in the HFC-32/HFO-1234yf refrigerant mixture is made to fall within the acceptable range of ±1.0% by weight of the target composition in a container or target equipment until transfer is complete, the upper limit of the HFC-32 composition in the liquid phase of the HFC-32/HFO-1234yf refrigerant blend immediately prior to transfer is 1.0% by weight of the target composition of HFC-32.

Also, when the mixture contains HFC-32 in an amount of 90% by weight, changes in the composition of HFC-32 are small; therefore, even when the initial composition of HFC-32 is approximately -0.5% by weight of the target composition (90% by weight), the proportion of HFC-32 in the liquid phase of the mixture falls within ±1.0% by weight of the target composition until the transfer is complete.

(1 -6) Method for filling a non-azeotropic refrigerant mixture composed of HFC-32 and HFO-1234yf

The concept of a filling method of the present invention is shown below, in relation to an embodiment carried out when a container is filled with a non-azeotropic refrigerant mixture composed of HFC-32 and HFO-1234yf in an amount < 100% by weight of the maximum filling quantity.

HFC-32 (wt%)

Equation (1) above can be derived from equations (2)-(5) above. Based on the value of each coefficient of Equations (2) -(5), L ¹ to P ¹ of Equation (1) can be calculated from the target composition (x) with respect to the established tolerance (a) .

A method of the present invention for filling a refrigerant mixture composed of HFC-32 and HFO-1234yf, the HFC-32 being present in a liquid phase in an amount of 10-90% by weight based on 100% by weight of the total of HFC-32 and HFO-1234yf, has the following feature. Specifically, when transferring the refrigerant mixture in a liquid state to a target container or equipment from a feed container, the proportion (initial composition) of 1HFC-32 in the liquid phase of the refrigerant mixture in the feed container is adjusted immediately before transfer axy ¹ % by weight (minimum value) axa % by weight (maximum value), so that the proportion of 1HFC-32 in the liquid phase of the refrigerant mixture in the feed container falls within a set tolerance (±a % by weight) of the target composition (x) of HFC-32 during the start and finish of the transfer.

In view of the concept of the present invention described above, when a = 1.5, and 32 < x < 42, then yC > a; therefore, x is within a range of 10-32 wt% or 42-90 wt%. Also, when a = 1.0 and 14 < x < 65, then yD > a; therefore, x is within a range of 10-14 wt% or 65-90 wt%.

±a: a set tolerance (a > 0);

x: an objective composition, with the condition that 10 < x < 90, which excludes an interval that satisfies the inequality: y ¹ > a

and ¹ : a lower bound on the difference between the target composition and the initial composition, and ¹ which is represented by Equation (1) below:

1000yi = L1X3 - M1X2 NiX - PL (1)

L1 = ^0.0002a 0.016

M1 = 0.072a ^3.4761

N1 = 7.914a ^187.52

P1 = ^1194.8a - 9.58.

(2) Filling method in which a refrigerant mixture is filled into a supply container in an amount < 70% by weight of the maximum filling amount calculated using a value obtained by dividing 1.05 by the specific gravity of the gas at 65 °C as the filling constant

The mixture ratio is described below in terms of a refrigerant mixture before being transferred to a target vessel or equipment from a feed vessel that is filled with the refrigerant mixture in an amount equal to 70% by weight of the maximum amount calculated using a value obtained by dividing 1.05 by the specific gravity of the gas at 65°C as the filling constant.

(2-1) Filling method that allows the composition of HFC-32 to fall within a range of ±a % by weight of the target composition (x) of HFC-32

A method (a gas transfer filling method) of the present invention for filling a refrigerant mixture composed of HFC-32 and HFO-1234yf such that HFC-32 is present in the liquid phase in an amount of 10- 90% by weight based on 100% by weight of total HFC-32 and HFO-1234yf, the method of transferring the refrigerant mixture in a liquid state to a target vessel or equipment from a feed vessel that is filled with the refrigerant mixture in an amount < 70% by weight of the maximum filling amount of the refrigerant mixture, it has the following characteristic. Specifically, the proportion (initial composition) of HFC-32 in the liquid phase of the refrigerant mixture in the feed vessel is adjusted immediately before transfer to axy ² wt% (minimum value) axa wt% (maximum value), so that the proportion of HFC-32 in the liquid phase of the refrigerant mixture in the feed vessel falls within a set tolerance (±a wt%) of the target composition (x) of HFC-32 during start-up and completion of the transfer.

±a: set tolerance (a > 0)

x: target composition (with the condition that 10 < x < 90, which excludes an interval that satisfies an inequality: y ² > a)

and ² : a lower bound of a difference between the target composition and the initial composition, and ² which is represented by Equation (6) below:

1000y2 = L2x3 - M2x2 N2x - P2 (6)

^l_2 = -0.0016 to 0.0169

M2 = ^-0.1765a 3.4316

^N2 = -1.87a 180.08

P2 = ^1119.5 to 148.9.

The "±a" (established tolerance) is a difference between a reference value (a target composition (x) of HFC-32) and a maximum or minimum acceptable value of the reference value. Specifically, "±a" is an acceptable difference relative to the target composition.

According to the method for filling a refrigerant mixture of the present invention, the proportion of HFC-32 in the liquid phase of the mixture in a feed container is adjusted before transfer to a specific range; Therefore, even when the feed vessel is initially filled with the cooling mixture in an amount equal to 70% by weight of the maximum filling amount of the cooling mixture, changes in composition in a target vessel or equipment fall within of an acceptable range, ie, ±a % by weight of the target composition, until the transfer is complete.

The HFC-32 "target composition" is the concentration of HFC-32 in the overall composition (liquid phase and vapor phase) of the HFC-32/HFO-1234yf refrigerant mixture, and is calculated in a target vessel or equipment .

The boiling point of HFC-32 is lower than that of HFO-1234yf. Therefore, when the space created due to refrigerant removal is refilled with vapor evaporated from the liquid phase during transfer, e1HFC-32 evaporates in a greater amount than that of HFO-1234yf, causing a reduction in the concentration of HFC-32 in the liquid phase. For this reason, HFC-32 is preferably filled into a feed container before transfer in an amount greater than that of the target composition. The a value above is usually set to 0.5 < a < 3.0. An example is described below with respect to a method that performs transfer at a handling temperature of 40°C. For the same reason as described above, even when the container is filled with the refrigerant mixture in an amount of 70% by weight of the maximum filling amount, the conditions for transfer at a handling temperature of 40 °C can be apply to conditions for transfer at a handling temperature of 0-40°C.

(2-2) Filling method that allows the composition of HFC-32 to fall within a range of ±2.5% by weight of the target composition (x) of HFC-32

Next, an embodiment is described in which the set tolerance (±a) is ±2.5.

In one embodiment of a method of the present invention for filling a refrigerant mixture composed of HFC-32 and HFO-1234yf such that HFC-32 is present in the liquid phase in an amount of 10-90% by weight based on 100 % by weight of the total of HFC-32 and HFO-1234yf, when transferring the refrigerant mixture in a liquid state to a target container or equipment from a feed container that is filled with the refrigerant mixture in an amount < 70% by weight of the maximum amount to fill the refrigerant mixture, the proportion (initial composition) of HFC-32 in the liquid phase of the refrigerant mixture in the feed container is preferably adjusted, before transfer, to x yE % by weight to x 2.5 % in weight, so that the proportion of HFC-32 in the liquid phase of the refrigerant mixture in the feed container falls within a range of ±2.5% by weight of the target composition (x) of HFC-32 during start-up and completion of the transfer a.

(In the above, x is a target composition, provided that 10 < x < 90; and yE is a lower bound on a difference between the target composition and the initial composition, and is represented by Equation (7):

1000yE = 0.013x3 - 3.0285X2 1 77. 93x - 2975.4 (7 ) . )

In this embodiment, referring to Equation (7) above, when transferring the refrigerant mixture of HFC-32/HFO-1234yf to a target vessel or equipment from a feed vessel, the proportion of HFC-32 in the liquid phase of the coolant mixture in the feed vessel is adjusted, prior to transfer, to about x - 2.0 wt% to x 2.5 wt%. Changes in composition in a target container or equipment may thus fall within the acceptable range of ±2.5% by weight of the target composition until transfer is complete.

The boiling point of HFC-32 is lower than that of HFO-1234yf. Therefore, when the space created due to refrigerant removal is filled with vapor evaporated from the liquid phase during transfer, e1HFC-32 evaporates in a greater amount than that of HFO-1234yf, causing a reduction in the concentration of HFC-32 in the liquid phase. For this reason, HFC-32 is preferably filled into a feed container before transfer in an amount greater than that of the target composition. In the method for filling a refrigerant mixture in which the HFC-32 composition in the HFC-32/HFO-1234yf refrigerant mixture is made to fall within the acceptable range of ±2.5% by weight of the target composition in a container or target equipment until transfer is complete, the upper limit of the HFC-32 composition in the liquid phase of the HFC-32/HFO-1234yf refrigerant mixture immediately prior to transfer is 2.5% by weight of the target composition of HFC-32.

Also, when the mixture contains HFC-32 in an amount of 90% by weight, changes in the composition of HFC-32 are small; therefore, even when the initial composition of HFC-32 is approximately -2.0% by weight of the target composition (90% by weight), the proportion of HFC-32 in the liquid phase of the mixture falls within ±2.5% by weight of the target composition until the transfer is complete.

(2-3) Filling method that allows the composition of HFC-32 to fall within a range of ±2.0% by weight of the target composition (x) of HFC-32

Next, an embodiment is described in which the set tolerance (±a) is ±2.0.

In one embodiment of a method of the present invention for filling a refrigerant mixture composed of HFC-32 and HFO-1234yf such that HFC-32 is present in the liquid phase in an amount of 10-90% by weight based on 100 % by weight of the total of HFC-32 and HFO-1234yf, when transferring the refrigerant mixture in a liquid state to a target container or equipment from a feed container that is filled with the refrigerant mixture in an amount < 70% by weight of the maximum filling amount of the refrigerant mixture, the proportion (initial composition) of HFC-32 in the liquid phase of the refrigerant mixture in the feed container is preferably adjusted, before transfer, to x yF % by weight to x 2.0 % by weight, so that the proportion of HFC-32 in the liquid phase of the refrigerant mixture in the feed vessel falls within a range of ±2.0% by weight of the target composition (x) of HFC-32 during start-up and completion of the transfer nce.

(In the above, x is a target composition, provided that 10 < x < 90; and yF is a lower bound on a difference between the target composition and the initial composition, and is represented by Equation (8):

1000yF = 0.0132X3 - 2.991x2 1 71 .39x - 2327.0 (8) .)

In this embodiment, referring to Equation (8) above, when transferring the refrigerant mixture of HFC-32/HFO-1234yf to a target vessel or equipment from a feed vessel, the proportion of HFC-32 in the liquid phase of the coolant mixture in the feed vessel is adjusted, prior to transfer, to about x - 1.5 wt% to x 2.0 wt%. Changes in composition in a target container or equipment may thus fall within the acceptable range of ±2.0% by weight of the target composition until transfer is complete.

For the same reason as described above, HFC-32 is preferably filled into a feed container before transfer in an amount greater than that of the target composition. In the method for filling a refrigerant mixture, in which the HFC-32 composition in the HFC-32/HFO-1234yf refrigerant mixture is made to fall within the acceptable range of ±2.0% by weight of the target composition in a container or target equipment until transfer is complete, the upper limit of the HFC-32 composition in the liquid phase of the HFC-32/HFO-1234yf refrigerant blend immediately prior to transfer is 2.0% by weight of the target composition of HFC-32.

Also, when the mixture contains HFC-32 in an amount of 90% by weight, changes in the composition of HFC-32 are small; therefore, even when the initial composition of HFC-32 is approximately -1.5% by weight of the target composition (90% by weight), the proportion of HFC-32 in the liquid phase of the mixture falls within ±2.0% by weight of the target composition until the transfer is complete.

(2-4) Filling method that allows the composition of HFC-32 to fall within a range of ±1.5% by weight of the target composition (x) of HFC-32

Next, an embodiment is described in which the set tolerance (±a) is ±1.5.

In one embodiment of a method of the present invention for filling a refrigerant mixture composed of HFC-32 and HFO-1234yf such that HFC-32 is present in the liquid phase in an amount of 10-90% by weight based on 100 % by weight of the total of HFC-32 and HFO-1234yf, when transferring the refrigerant mixture in a liquid state to a target container or equipment from a feed container that is filled with the refrigerant mixture in an amount < 70% by weight of the maximum filling quantity of the refrigerant mixture, the proportion (initial composition) of HFC-32 in the liquid phase of the refrigerant mixture in the feed container is preferably adjusted, before transfer, to x yG % by weight to x 1.5 % by weight, so that the proportion of HFC-32 in the liquid phase of the refrigerant mixture in the feed vessel is within a range of ±1.5% by weight of the target composition (x) of HFC-32 during start-up and the completion of the transfer rence.

(In the above, x is a target composition, provided that 10 < x < 90; and yG is a lower bound on a difference between the target composition and the initial composition, and is represented by Equation (9):

1000yG = 0.0149X3 - 3.2273x2 179.57x - 1866.7 (9) ).

In this embodiment, referring to Equation (9) above, when transferring the refrigerant mixture of HFC-32/HFO-1234yf to a target vessel or equipment from a feed vessel, the proportion of HFC-32 in the liquid phase of the coolant mixture in the feed vessel is adjusted, prior to transfer, to about x - 1.0 wt% to x 1.5 wt%. Changes in composition in a target container or equipment may thus fall within the acceptable range of ±1.5% by weight of the target composition until transfer is complete.

For the same reason as described above, HFC-32 is preferably filled into a feed container before transfer in an amount greater than that of the target composition. In the method for filling a refrigerant mixture, in which the HFC-32 composition in the HFC-32/HFO-1234yf refrigerant mixture is made to fall within the acceptable range of ±1.5% by weight of the target composition in a container or target equipment until transfer is complete, the upper limit of the HFC-32 composition in the liquid phase of the HFC-32/HFO-1234yf refrigerant mixture immediately prior to transfer is 1.5% by weight of the target composition of HFC-32.

Also, when the mixture contains HFC-32 in an amount of 90% by weight, changes in the composition of HFC-32 are small; therefore, even when the initial composition of HFC-32 is approximately -1.0% by weight of the target composition (90% by weight), the proportion of HFC-32 in the liquid phase of the mixture falls within ±1.5% by weight of the target composition until the transfer is complete.

(2-5) Filling method that allows the composition of HFC-32 to fall within a range of ±1.0% by weight of the target composition (x) of HFC-32

Next, an embodiment is described in which the set tolerance (±a) is ±1.0.

In an embodiment of a method of the present invention for filling a refrigerant mixture composed of HFC-32 and HFO-1234yf in such a way that HFC-32 is present in the liquid phase in an amount of 10-18% by weight or 60 -90 wt% based on 100 wt% of total HFC-32 and HFO-1234yf, when transferring the refrigerant mixture in a liquid state to a target vessel or equipment from a feed vessel that is filled with the refrigerant mixture in an amount < 70% by weight of the maximum filling amount of the refrigerant mixture, the proportion (initial composition) of HFC-32 in the liquid phase of the refrigerant mixture in the feed container is preferably adjusted, before transfer, a x yH wt% a x 1.0 wt%, so that the proportion of HFC-32 in the liquid phase of the refrigerant mixture in the feed vessel falls within a range of ±1.0 wt% of the target composition (x) of HFC-32 during start-up and end ization of the transfer. When a = 1.0 and 18 < x < 60, then yH > a; therefore, x is within a range of 10-18 wt% or 60-90 wt%.

(In the above, x is as defined above; and yH is a lower bound on a difference between the target composition and the initial composition, and is represented by Equation (10):

1000yH = 0.0151X3 - 3.2439X2 1 78 .32x - 1263.0 (10) . )

In this embodiment, referring to Equation (10) above, when transferring the refrigerant mixture of HFC-32/HFO-1234yf to a target vessel or equipment from a feed vessel, the proportion of HFC-32 in the liquid phase of the coolant mixture in the feed vessel is adjusted, prior to transfer, to about x - 0.5 wt% to x 1.0 wt%. Changes in composition in a target container or equipment may thus fall within the acceptable range of ±1.0% by weight of the target composition until transfer is complete.

For the same reason as described above, HFC-32 is preferably filled into a feed container before transfer in an amount greater than that of the target composition. In the method of filling a refrigerant mixture, in which the HFC-32 composition in the HFC-32/HFO-1234yf refrigerant mixture is made to fall within the acceptable range of ±1.0% by weight of the target composition in a target vessel or equipment until transfer is complete, the upper limit of the composition of HFC-32 in the phase HFC-32/HFO-1234yf refrigerant blend liquid immediately prior to transfer is 1.0% by weight of the HFC-32 target composition.

Also, when the mixture contains HFC-32 in an amount of 90% by weight, changes in the composition of HFC-32 are small; therefore, even when the initial composition of HFC-32 is approximately -0.5% by weight of the target composition (90% by weight), the proportion of HFC-32 in the liquid phase of the mixture falls within ±1.0% by weight of the target composition until the transfer is complete.

(2-6) Method for filling a non-azeotropic refrigerant mixture composed of HFC-32 and HFO-1234yf

The concept of a filling method of the present invention is shown below, in relation to an embodiment carried out when a container is filled with a non-azeotropic refrigerant mixture composed of HFC-32 and HFO-1234yf in an amount < 70% by weight of the maximum filling quantity.

HFC-32 (wt%)

Equation (6) above can be derived from Equations (7)-(10) above. Based on the value of each coefficient of Equations (7) -(10), L ² to P ² of Equation (6) can be calculated from the target composition (x) with respect to the established tolerance (a) .

A method of the present invention for filling a refrigerant mixture composed of HFC-32 and HFO-1234yf, the HFC-32 being present in a liquid phase in an amount of 10-90% by weight based on 100% by weight of the total of HFC-32 and HFO-1234yf has the following characteristic. Specifically, when transferring the refrigerant mixture in a liquid state to a target container or equipment from a feed container that is filled with the refrigerant mixture in an amount < 70% by weight of the maximum filling amount of the refrigerant mixture, the proportion (initial composition) of HFC-32 in the liquid phase of the refrigerant mixture in the feed vessel is adjusted immediately before transfer to axy ² % by weight (minimum value) axa % by weight (maximum value), so that the proportion of HFC-32 in the liquid phase of the refrigerant mixture in the feed vessel may fall within a set tolerance (±a wt%) of the target composition (x) of HFC-32 during the start and finish of the transfer. In view of the concept of the present invention described above, when a = 1.0 and 18 < x < 60, then yH >a; therefore, x is within a range of 10-18 wt% or 60-90 wt%.

±a: a set tolerance (a > 0);

x: an objective composition, with the condition that 10 < x < 90, which excludes an interval that satisfies the inequality: y ² > a

and ² : a lower bound on the difference between the target composition and the initial composition, and ² which is represented by Equation (6) below:

1000y2 = L2x3 - M2x2 N2x - P2 (6)

^L2 = -0.0016a 0.0169

M2 = ^-0.1765a 3.4316

^N2 = -1.87a 180.08

P2 = ^1119.5 to 148.9.

(3) Filling method in which a refrigerant mixture is filled into a feeding container in an amount of the maximum filling amount calculated using a value obtained by dividing 1.05 by the specific gravity of the gas at 45 °C as the filling constant .

The mix ratio is described below in terms of a coolant mix before it is transferred to a target vessel or equipment from a feed container that is filled with the coolant mix in an amount < 100% by weight of the maximum amount of calculated using a value obtained by dividing 1.05 by the specific gravity of the gas at 45 °C as the filling constant.

(3-1) Filling method that allows the composition of HFC-32 to fall within a range of ±a % by weight of the target composition (x) of HFC-32

A method (a gas transfer filling method) of the present invention for filling a refrigerant mixture composed of HFC-32 and HFO-1234yf such that HFC-32 is present in the liquid phase in an amount of 10- 90% by weight based on 100% by weight of total HFC-32 and HFO-1234yf, the method of transferring the refrigerant mixture in a liquid state to a target vessel or equipment from a feed vessel that is full with the refrigerant mixture, it has the following characteristic. Specifically, the proportion (initial composition) of HFC-32 in the liquid phase of the refrigerant mixture in the feed vessel is adjusted immediately before transfer to axy ³ wt% (minimum value) axa wt% (maximum value), so that the proportion of HFC-32 in the liquid phase of the refrigerant mixture in the feed vessel falls within a set tolerance (±a wt%) of the target composition (x) of HFC-32 during start-up and completion of the transfer.

±a: tolerance setting (a > ⁰ )

x: target composition (provided that 10 < x < 90, which excludes an interval that satisfies an inequality: y ³ > a)

and ³ : a lower bound on the difference between the target composition and the initial composition, and ³ which is represented by Equation (11) below:

1000y3 = L3x3 - M3x2 N3x - P3 (11)

L3 = ^0.0003a 0.0172

M3 = 0.0962a ^3.6851

N3 = ^9.704a 196.9

^P3 = 1241.2a - 93.54.

The "±a" (established tolerance) is a difference between a reference value (a target composition (x) of HFC-32) and a maximum or minimum acceptable value of the reference value. Specifically, "±a" is an acceptable difference relative to the target composition.

According to the method for filling a refrigerant mixture of the present invention, the proportion of HFC-32 in the liquid phase of the mixture in a feed container is adjusted before transfer to a specific range; therefore, even when the feed vessel is filled with the cooling mixture in an amount of ¹⁰⁰ % by weight of the maximum filling amount of the cooling mixture, changes in composition in a target vessel or equipment fall within an acceptable range, ie, ±a wt% of the target composition, until transfer is complete.

The HFC-32 "target composition" is the concentration of HFC-32 in the overall composition (liquid phase and vapor phase) of the HFC-32/HFO-1234yf refrigerant mixture, and is calculated in a target vessel or equipment .

The boiling point of HFC-32 is lower than that of HFO-1234yf. Therefore, when the space created due to refrigerant removal is filled with vapor evaporated from the liquid phase during transfer, e1HFC-32 evaporates in a greater amount than that of HFO-1234yf, causing a reduction in the concentration of HFC-32 in the liquid phase. For this reason, HFC-32 is preferably filled into a feed container before transfer in an amount greater than that of the target composition. The a value above is usually set to 0.5 < a < 3.0.

An example is described below with respect to a method that performs transfer at a handling temperature of 40°C. For example, according to Japan's High Pressure Gas Safety Legislation, etc., it is prohibited to handle a container at a temperature of 40 °C or more; therefore, the handling temperature is basically 0-40°C when the transfer is done. A higher temperature during the transfer (at the time of handling) causes a larger compositional change associated with the transfer. Therefore, the conditions for transfer at a handling temperature of 40°C can also be applied to the conditions for transfer at a handling temperature of 0-40°C.

(3-2) Filling method that allows the composition of HFC-32 to fall within a range of ±2.5% by weight of the target composition (x) of HFC-32

Next, an embodiment is described in which the set tolerance (±a) is ±2.5.

In one embodiment of a method of the present invention for filling a refrigerant mixture composed of HFC-32 and HFO-1234yf such that HFC-32 is present in the liquid phase in an amount of 10-90% by weight based on 100 % by weight of total HFC-32 and HFO-1234yf, when transferring the refrigerant mixture in a liquid state to a target vessel or equipment from a feed vessel, the proportion (initial composition) of HFC-32 in the liquid phase of the refrigerant mixture in the feed vessel is preferably adjusted, before transfer, from x to ¹ wt% to x 2.5 wt %, so that the proportion of HFC-32 in the liquid phase of the refrigerant mixture in the feed vessel falls within a range of ±2.5% by weight of the composition target (x) of HFC-32 during the start and the end of the transfer.

(In the above, x is a target composition, provided that 10 < x < 90; and yI is a lower bound on a difference between the target composition and the initial composition, and is represented by Equation (12):

1000yz = 0.0181X3 - 3.9611x2 223 . lx-3040.4(12). )

In this embodiment, referring to Equation (12) above, when transferring the refrigerant mixture of HFC-32/HFO-1234yf to a target vessel or equipment from a feed vessel, the proportion of HFC-32 in the liquid phase of the coolant mixture in the feed vessel is adjusted, prior to transfer, to x - 1.8 wt% to x 2.5 wt%. Changes in composition in a target container or equipment may thus fall within the acceptable range of ±2.5% by weight of the target composition until transfer is complete.

The boiling point of HFC-32 is lower than that of HFO-1234yf. Therefore, when the space created due to refrigerant removal is filled with vapor evaporated from the liquid phase during transfer, e1HFC-32 evaporates in a greater amount than that of HFO-1234yf, causing a reduction in the concentration of HFC-32 in the liquid phase. For this reason, HFC-32 is preferably filled into a feed container before transfer in an amount greater than that of the target composition. In the method for filling a refrigerant mixture in which the HFC-32 composition in the HFC-32/HFO-1234yf refrigerant mixture is made to fall within the acceptable range of ±2.5% by weight of the target composition in a container or target equipment until transfer is complete, the upper limit of the HFC-32 composition in the liquid phase of the HFC-32/HFO-1234yf refrigerant mixture immediately prior to transfer is 2.5% by weight of the target composition of HFC-32.

Also, when the mixture contains HFC-32 in an amount of 90% by weight, changes in the composition of HFC-32 are small; therefore, even when the initial composition of HFC-32 is approximately -1.8% by weight of the target composition (90% by weight), the proportion of HFC-32 in the liquid phase of the mixture falls within ±2.5% by weight of the target composition until the transfer is complete.

(3-3) Filling method that allows the composition of HFC-32 to fall within a range of ±2.0% by weight of the target composition (x) of HFC-32

Next, an embodiment is described in which the set tolerance (±a) is ±2.0.

In one embodiment of a method of the present invention for filling a refrigerant mixture composed of HFC-32 and HFO-1234yf such that HFC-32 is present in the liquid phase in an amount of 10-90% by weight based on 100 % by weight of total HFC-32 and HFO-1234yf, when transferring the refrigerant mixture in a liquid state to a target vessel or equipment from a feed vessel, the proportion (initial composition) of HFC-32 in the liquid phase of the refrigerant mixture in the feed vessel is preferably adjusted, prior to transfer, at x yj wt% to x 2.0 wt%, so that the proportion of HFC-32 in the liquid phase of the refrigerant mixture in the feed vessel falls within a range of ±2.0% by weight of the target composition (x) of HFC-32 during the start and finish of the transfer.

(In the above, x is a target composition, provided that 10 < x < 90; and yj is a lower bound on a difference between the target composition and the initial composition, and is represented by Equation (13):

l O O O y j = 0.0177X3 - 3.8614x2 2 15. 42x - 2373.5 (13) .)

In this embodiment, referring to Equation (13) above, when transferring the refrigerant mixture of HFC-32/HFO-1234yf to a target vessel or equipment from a feed vessel, the proportion of HFC-32 in the liquid phase of the coolant mixture in the feed vessel is adjusted, prior to transfer, to about x - 1.3 wt% to x 2.0 wt%. Changes in composition in a target container or equipment may thus fall within the acceptable range of ±2.0% by weight of the target composition until transfer is complete.

For the same reason as described above, HFC-32 is preferably filled into a feed container before transfer in an amount greater than that of the target composition. In the method for filling a refrigerant mixture, in which the HFC-32 composition in the HFC-32/HFO-1234yf refrigerant mixture is made to fall within the acceptable range of ±2.0% by weight of the target composition in a container or target equipment until transfer is complete, the upper limit of the HFC-32 composition in the liquid phase of the HFC-32/HFO-1234yf refrigerant blend immediately prior to transfer is 2.0% by weight of the target composition of HFC-32.

Also, when the mixture contains HFC-32 in an amount of 90% by weight, changes in the composition of HFC-32 are small; therefore, even when the initial composition of HFC-32 is approximately -1.3% by weight of the target composition (90% by weight), the proportion of HFC-32 in the liquid phase of the mixture falls within ±2.0% by weight of the target composition until the transfer is complete.

(3-4) Filling method that allows the composition of HFC-32 to fall within a range of ±1.5% by weight of the target composition (x) of HFC-32

Next, an embodiment is described in which the set tolerance (±a) is ±1.5.

In an embodiment of a method of the present invention for filling a refrigerant mixture composed of HFC-32 and HFO-1234yf such that HFC-32 is present in the liquid phase in an amount of 10-26.5% by weight or 47.5- 90% by weight based on 100% by weight of the total of HFC-32 and HFO-1234yf, when transferring the refrigerant mixture in a liquid state to a target vessel or equipment from a feed vessel, the proportion (initial composition) of HFC -32 in the liquid phase of the refrigerant mixture in the feed vessel is preferably adjusted, before transfer, at x and x wt% to x 1.5 wt%, so that the proportion of HFC-32 in the liquid phase of the mixture refrigerant in the feed vessel falls within ±1.5% by weight of the target composition (x) of HFC-32 during the start and finish of the transfer. When a = 1.5, and 26.5 < x < 47.5, then yx > a; therefore, x is within a range of 10-26.5 wt% or 47.5-90 wt%. (In the above, x is a target composition; and yx is a lower bound on a difference between the target composition and the initial composition, and is represented by Equation (14):

1000yK = 0.0172X3 - 3.7549x2 207 .43x - 1705.9 (14) .)

In this embodiment, referring to Equation (14) above, when transferring the refrigerant mixture of HFC-32/HFO-1234yf to a target vessel or equipment from a feed vessel, the proportion of HFC-32 in the liquid phase of the coolant mixture in the feed vessel is adjusted, prior to transfer, to about x - 0.9 wt% to x 1.5 wt%. Changes in composition in a target container or equipment may thus fall within the acceptable range of ±1.5% by weight of the target composition until transfer is complete.

For the same reason as described above, HFC-32 is preferably filled into a feed container before transfer in an amount greater than that of the target composition. In the method for filling a refrigerant mixture, in which the HFC-32 composition in the HFC-32/HFO-1234yf refrigerant mixture is made to fall within the acceptable range of ±1.5% by weight of the target composition in a container or target equipment until transfer is complete, the upper limit of the HFC-32 composition in the liquid phase of the HFC-32/HFO-1234yf refrigerant mixture immediately prior to transfer is 1.5% by weight of the target composition of HFC-32.

Also, when the mixture contains HFC-32 in an amount of 90% by weight, changes in the composition of HFC-32 are small; therefore, even when the initial composition of HFC-32 is approximately -0.9% by weight of the target composition (90% by weight), the proportion of HFC-32 in the liquid phase of the mixture falls within ±1.5% by weight of the target composition until the transfer is complete.

(3-5) Filling method that allows the composition of HFC-32 to fall within a range of ±1.0% by weight of the target composition (x) of HFC-32

Next, an embodiment is described in which the set tolerance (±a) is ±1.0.

In an embodiment of a method of the present invention for filling a refrigerant mixture composed of HFC-32 and HFO-1234yf such that HFC-32 is present in the liquid phase in an amount of 10-13.5% by weight or 67 90 % by weight based on 100% by weight of the total of HFC-32 and HFO-1234yf, when transferring the refrigerant mixture in a liquid state to a target vessel or equipment from a feed vessel, the proportion (initial composition) of HFC- 32 in the liquid phase of the refrigerant mixture in the feed vessel is preferably adjusted, prior to transfer, to x yL wt% to x 1.0 wt%, so that the proportion of HFC-32 in the liquid phase of the refrigerant mixture in the feed vessel falls within a range of ±1.0% by weight of the target composition (x) of HFC-32 during the start and finish of the transfer. When a = 1.0, and 13.5 < x < 67, then yL > a; therefore, x is within a range of 10-13.5 wt% or 67-90 wt%.

(In the above, x is as defined above, with the proviso that 10 < x < 13.5 or 67 < x < 90; and yL is a lower bound on a difference between the target composition and the initial composition, and is represented by Equation (5):

[0253] 1000yL = 0.0178x3 - 3.8363x2 209 .59x - 1194.3 (15) . )

In this embodiment, referring to Equation (15) above, when transferring the refrigerant mixture of HFC-32/HFO-1234yf to a target vessel or equipment from a feed vessel, the proportion of HFC-32 in the liquid phase of the coolant mixture in the feed vessel is adjusted, prior to transfer, to about x - 0.4 wt% to x 1.0 wt%. Changes in composition in a target container or equipment may thus fall within the acceptable range of ±1.0% by weight of the target composition until transfer is complete.

For the same reason as described above, HFC-32 is preferably filled into a feed container before transfer in an amount greater than that of the target composition. In the method for filling a refrigerant mixture, in which the HFC-32 composition in the HFC-32/HFO-1234yf refrigerant mixture is made to fall within the acceptable range of ±1.0% by weight of the target composition in a container or target equipment until transfer is complete, the upper limit of the HFC-32 composition in the liquid phase of the HFC-32/HFO-1234yf refrigerant blend immediately prior to transfer is 1.0% by weight of the target composition of HFC-32.

Also, when the mixture contains HFC-32 in an amount of 90% by weight, changes in the composition of HFC-32 are small; therefore, even when the initial composition of HFC-32 is approximately -0.4% by weight of the target composition (90% by weight), the proportion of HFC-32 in the liquid phase of the mixture falls within ±1.0% by weight of the target composition until the transfer is complete.

(3-6) Method for filling a non-azeotropic refrigerant mixture composed of HFC-32 and HFO-1234yf

The concept of a method of filling the present invention is shown below, in relation to an embodiment carried out when a container is filled with a non-azeotropic refrigerant mixture composed of HFC-32 and HFO-1234yf in an amount < 100% by weight of the maximum amount of filling.

0 to 13.5 S26.5 47.5 to 67 to 100

HFC-32 (wt%)

Equation (11) above can be derived from Equations (12) - (15) above. Based on the value of each coefficient of Equations (12) -(15), L ³ to P ³ of Equation (11) can be calculated from the target composition (x) with respect to the established tolerance (a) .

A method of the present invention for filling a refrigerant mixture composed of HFC-32 and HFO-1234yf, the HFC-32 being present in a liquid phase in an amount of 10-90% by weight based on 100% by weight of the total of HFC-32 and HFO-1234yf has the following feature. Specifically, when transferring the refrigerant mixture in a liquid state to a target container or equipment from a feed container, the proportion (initial composition) of 1HFC-32 in the liquid phase of the refrigerant mixture in the feed container is adjusted immediately before transfer to x and 3% by weight (minimum value) to x a % by weight (maximum value), so that the proportion of 1HFC-32 in the liquid phase of the refrigerant mixture in the feed container can fall within a set tolerance (±a % by weight) of the target composition (x) of HFC-32 during the start and the end of the transfer.

In view of the concept of the present invention described above, when a = 1.5 and 26.5 < x < 47.5, then yK > a; therefore, x is within a range of 10-26.5 wt% or 47.5-90 wt%. Also, when a = 1.0, and 13.5 < x < 67, then yL > a; therefore, x is within a range of 10-13.5 wt% or 67-90 wt%. ±a: a set tolerance (a > 0);

x: an objective composition, with the condition that 10 < x < 90, which excludes an interval that satisfies the inequality: y3 > a

y3: a lower bound on the difference between the target composition and the initial composition, y3 which is represented by Equation (11) below:

1000y3 = L3x3 - M3x2 N3x - P3 (11)

L3 = ^0.0003a 0.0172

M3 = 0.0962a ^3.6851

N3 = ^9.704a 196.9

^P3 = 1241.2a - 93.54.

(4) Filling method in which the refrigerant mixture is filled into a container in an amount less than the filling amount calculated using a value obtained by dividing 1.05 by the specific gravity of the gas at 45°C as the filling constant, and greater than 70% by weight of the filling amount calculated using a value obtained by dividing 1.05 by the specific gravity of the gas at 65°C as the filling constant

In the transfer of an HFC-32/HFO-1234yf refrigerant mixture to a target vessel or equipment from a feed vessel, a smaller amount of the mixture than was initially filled into the feed vessel results in a smaller change in temperature. composition of HFC-32 in the liquid phase of the refrigerant mixture in the feed vessel during the start and finish of the transfer.

In terms of transfer of a refrigerant mixture of HFC-32/HFO-1234yf, from the point of view of a coolant mix as a product, transfer is less likely to occur when a feed vessel is initially filled with coolant mix in an amount < 70% by weight of the maximum fill amount. Specifically, when the transfer is made, the filling is assumed to be 70-100% by weight. Therefore, the conditions for transfer are realized when the amount to fill the refrigerant mixture is 70% by weight of the maximum filling amount calculated using a value obtained by dividing 1.05 by the specific gravity of the gas at 65 °C as the constant of filling, and the conditions can be applied for the transfer made when the quantity to fill the refrigerant mixture is 100% by weight of the maximum filling quantity calculated using a value obtained by dividing 1.05 by the specific gravity of the gas at 45 °C as the filling constant to obtain the conditions for the transfer carried out when the quantity to fill the refrigerant mixture is in a range between 70% by weight of the maximum filling quantity calculated using a value obtained by dividing 1.05 by the specific gravity of the gas to 65 °C as the fill constant and 100% by weight of the maximum fill amount calculated using a value obtained by dividing 1.05 by the specific gravity of the gas at 45 °C as the filling constant.

[2] Filling method for each set tolerance

The mix ratio is described below in terms of a coolant mix before it is transferred to a target vessel or equipment from a feed container that is filled with the coolant mix in an amount of a maximum fill amount (100% by weight). weight of a maximum filling quantity) of the refrigerant mixture.

The term "maximum fill quantity" (100% by weight of the maximum fill quantity) used in this specification refers to a maximum quantity that can be filled in a container, as defined in international legislation regarding the transport or in Japan's High Pressure Gas Safety Legislation. According to Japan's High Pressure Gas Safety Legislation, the maximum filling quantity is calculated as follows:

- G = V/C

- G: Mass (kg) of fluorocarbon

- V: Capacity (L) of the container

- C: Constant depending on the type of fluorocarbon

The filling constant C is determined here in Japan as a value obtained by dividing 1.05 by the specific gravity of the gas at 48°C. When it comes to export, according to international law, the filling constant C is defined as a value obtained by dividing 1.05 by the specific gravity of the gas at 65 °C when passing through tropical regions, and is defined as a value obtained by dividing 1.05 by the specific gravity of the gas at 45 °C when only non-tropical regions are involved.

In the transfer of an HFC-32/HFO-1234yf refrigerant mixture to a target vessel or equipment from a feed vessel, a smaller amount of the mixture than was initially filled into the feed vessel results in a smaller change in temperature. composition of HFC-32 in the liquid phase of the refrigerant mixture in the feed vessel during the start and finish of the transfer.

In the following, the maximum filling amount (100% by weight of the maximum filling amount) of the refrigerant mixture refers to a value calculated using a filling constant obtained by dividing 1.05 by the specific gravity of the gas at 45 °C.

(1) Filling method (stated tolerance (±a): ±2.0% by weight)

The mixing ratio is described below in terms of a coolant mixture before it is transferred to a target vessel or equipment from a feed vessel. The use of the blend ratio allows the proportion of HFC-32 in the liquid phase of the refrigerant blend in the feed vessel to fall within a range of ±2.0% by weight of the target composition (x) of HFC-32. 32 during the start and end of the transfer.

The "±a" (established tolerance) is a difference between a reference value (a target composition (x) of HFC-32) and a maximum or minimum acceptable value of the reference value. Specifically, "±a" is an acceptable difference relative to the target composition.

The HFC-32 "target composition" is the concentration of HFC-32 in the overall composition (liquid phase and vapor phase) of the HFC-32/HFO-1234yf refrigerant mixture, and is calculated in a target vessel or equipment .

(1-1) Filling method that allows the composition of HFC-32 to fall within a range of ±2.0% by weight of the target composition (x) of HFC-32

A method (a gas transfer filling method) of the present invention for filling a refrigerant mixture composed of HFC-32 and HFO-1234yf such that HFC-32 is present in the liquid phase in an amount of 10-90% by weight based on 100% by weight of the total of HFC-32 and HFO-1234yf, the method of transferring the refrigerant mixture in a liquid state to a target container or equipment from a container which is filled with the refrigerant mixture in an arbitrarily adjusted amount has the following characteristic. Specifically, the proportion (initial composition) of HFC-32 in the liquid phase of the refrigerant mixture in the feed vessel is adjusted immediately before the transfer to xy ⁴ % by weight (minimum value) to x 2.0% by weight (maximum value) , so that the proportion of HFC-32 in the liquid phase of the refrigerant mixture in the feed container falls within a range of ± ^{2 . 0} % by weight of a target composition (x) of HFC-32 during the start and finish of the transfer.

b: an amount (% by weight) initially filled in the feeding container

x: target composition (provided that 10 < x < 90, which excludes an interval that satisfies an inequality: y4 > ² )

and ⁴ : a lower bound on the difference between the target composition and the initial composition, and ⁴ which is represented by Equation (16) below:

1000y4 = L4 ^x 3 - M4 ^x 2 N4 ^x - P4 (16)

L4 = 0.0001b ^0.0081

M4 = 0.0195b 1.958

N4 = 0.9878b 118.91

P4 = -0.176b 2408.7.

According to the method for filling a refrigerant mixture of the present invention, the proportion of HFC-32 in the liquid phase of the mixture in a feed container is adjusted, before transfer, to a specific range; therefore, even when the feed vessel is filled with the coolant mixture in an amount of ¹⁰⁰ % by weight of the maximum filling amount, changes in composition in a target vessel or equipment fall within an acceptable range, i.e. say, ± ^{2 . 0} % by weight of the target composition, until the transfer is complete.

The boiling point of HFC-32 is lower than that of HFO-1234yf. Therefore, when the space created due to refrigerant removal is filled with vapor evaporated from the liquid phase during transfer, e1HFC-32 evaporates in a greater amount than that of HFO-1234yf, causing a reduction in the concentration of HFC-32 in the liquid phase. For this reason, HFC-32 is preferably filled into a feed container before transfer in an amount greater than that of the target composition.

The b value above is usually set to 60 < b < 100.

An example is described below with respect to a method that performs transfer at a handling temperature of 40°C. For example, according to Japan's High Pressure Gas Safety Legislation, it is prohibited to handle a container at a temperature of 40°C or higher; therefore, particularly in Japan, the handling temperature is 0-40°C when transferring. A higher temperature during the transfer (at the time of handling) causes a larger compositional change associated with the transfer. Therefore, the conditions for transfer at a handling temperature of 40°C can be applied to the conditions for transfer at a handling temperature of 0-40°C.

Also, with respect to the filling quantity in a feeding container, when the refrigerant mixture in a liquid state is transferred to a target container or equipment from the feeding container, a smaller initial filling quantity results in a composition change. minor associated with the transfer during the start and end of the transfer. Therefore, an equation that satisfies a filling method in which the initial fill amount is b wt% is also satisfied in a filling method in which the initial fill amount is b wt% or less. For example, an equation that satisfies a filling method in which the initial fill amount is ¹⁰⁰ % by weight is also satisfied in a filling method in which the initial fill amount is 100-0% by weight. An equation that satisfies a filling method in which the initial filling amount is 90% by weight is also satisfied in a filling method in which the initial filling amount is 90-0% by weight. An equation that satisfies a filling method in which the initial fill amount is 80 wt% is also satisfied in a filling method in which the initial fill amount is 80-0 wt%. An equation that satisfies a filling method in which the initial fill amount is 70 wt% is also satisfied in a filling method in which the initial fill amount is 70-0 wt%. An equation that satisfies a filling method in which the initial fill amount is 60 wt% is also satisfied in a filling method in which the initial fill amount is 60-0 wt%.

(1-2) Filling method in which the refrigerant mixture is filled into a container in an amount of 100% by weight of the maximum filling amount

Next, an embodiment is described in which the refrigerant mixture is filled into a container in an amount of 100% by weight of the maximum filling amount of the refrigerant mixture and in which the composition of HFC-32 is within a range of ±2.0% by weight of the target composition (x) of HFC-32 during the start and finish of the transfer.

In one embodiment of a method of the present invention for filling a refrigerant mixture composed of HFC-32 and HFO-1234yf such that HFC-32 is present in the liquid phase in an amount of 10-90% by weight based on 100 % by weight of the total of HFC-32 and HFO-1234yf, when transferring the refrigerant mixture in a liquid state to a target container or equipment from a feed container that is filled with the refrigerant mixture in an amount < 100% by weight of the maximum filling quantity of the refrigerant mixture, the proportion (initial composition) of HFC-32 in the liquid phase of the refrigerant mixture in the feed container is preferably adjusted, before transfer, to x yp ¹ % by weight to x 2.0 % by weight, so that the proportion of HFC-32 in the liquid phase of the refrigerant mixture in the feed vessel falls within a range of ±2.0% by weight of a target composition (x) of HFC-32 during startup and the completion of the transfer rence.

(In the above, x is a target composition, with the proviso that 10 < x <90; and yp ¹ is a lower bound on a difference between the target composition and the initial composition, and is represented by Equation (17) :

1000ypi = 0.0177X3 - 3.8614x2 215.42x - 2373.5 (17).)

In this embodiment, referring to Equation (17) above, when transferring the refrigerant mixture of HFC-32/HFO-1234yf to a target vessel or equipment from a feed vessel, the proportion of HFC-32 in the liquid phase of the coolant mixture in the feed vessel is adjusted, prior to transfer, to about x - 1.3 wt% to x 2.0 wt%. Changes in composition in a target container or equipment may thus fall within the acceptable range of ±2.0% by weight of the target composition until transfer is complete.

The boiling point of HFC-32 is lower than that of HFO-1234yf. Therefore, when the space created due to refrigerant removal is filled with vapor evaporated from the liquid phase during transfer, e1HFC-32 evaporates in a greater amount than that of HFO-1234yf, causing a reduction in the concentration of HFC-32 in the liquid phase. For this reason, HFC-32 is preferably filled into a feed container before transfer in an amount greater than that of the target composition. In the method for filling a refrigerant mixture in which the HFC-32 composition in the HFC-32/HFO-1234yf refrigerant mixture is made to fall within the acceptable range of ±2.0% by weight of the target composition in a container or target equipment until transfer is complete, the upper limit of the HFC-32 composition in the liquid phase of the HFC-32/HFO-1234yf refrigerant mixture immediately prior to transfer is 2.0% by weight of the target composition of HFC-32.

Also, when the mixture contains HFC-32 in an amount of 90% by weight, changes in the composition of HFC-32 are small; therefore, even when the initial composition of HFC-32 is approximately -1.3% by weight of the target composition (90% by weight), the proportion of HFC-32 in the liquid phase of the mixture falls within ±2.0% by weight of the target composition until the transfer is complete.

(1-3) Filling method in which the refrigerant mixture is filled into a container in an amount of 90% by weight of the maximum filling amount

Next, an embodiment is described in which the refrigerant mixture is filled into a container in an amount of 90% by weight of the maximum filling amount of the refrigerant mixture and in which the composition of HFC-32 falls within a range of ±2.0% by weight of the target composition (x) of HFC-32 during the start and finish of the transfer.

In one embodiment of a method of the present invention for filling a refrigerant mixture composed of HFC-32 and HFO-1234yf such that HFC-32 is present in the liquid phase in an amount of 10-90% by weight based on 100 % by weight of the total of HFC-32 and HFO-1234yf, when transferring the refrigerant mixture in a liquid state to a target container or equipment from a feed container that is filled with the refrigerant mixture in an amount < 90% by weight of the maximum filling quantity of the refrigerant mixture, the proportion (initial composition) of HFC-32 in the liquid phase of the refrigerant mixture in the feed container is preferably adjusted, before transfer, to x yp ² % by weight to x 2.0 % by weight, so that the proportion of HFC-32 in the liquid phase of the refrigerant mixture in the feed vessel falls within a range of ±2.0 % by weight of a target composition (x) of HFC-32 during startup and the completion of the transfer rence.

(In the above, x is a target composition, provided that 10 < x <90; and yp ² is a lower bound on a difference between the target composition and the initial composition, and is represented by Equation (18) :

1000yP2 = 0.0172X3 - 3.7532x2 210.lx - 2419.3 (18).)

In this embodiment, referring to Equation (18) above, when transferring the refrigerant mixture of HFC-32/HFO-1234yf to a target vessel or equipment from a feed vessel, the proportion of HFC-32 in the liquid phase of the coolant mixture in the feed vessel is adjusted, prior to transfer, to about x - 1.3 wt% to x 2.0 wt%. Changes in composition in a target container or equipment may thus fall within the acceptable range of ±2.0% by weight of the target composition until transfer is complete.

The boiling point of HFC-32 is lower than that of HFO-1234yf. Therefore, when the space created due to refrigerant removal is filled with vapor evaporated from the liquid phase during transfer, e1HFC-32 evaporates in a greater amount than that of HFO-1234yf, causing a reduction in the concentration of HFC-32 in the liquid phase. For this reason, HFC-32 is preferably filled into a feed container before transfer in an amount greater than that of the target composition. In the method for filling a refrigerant mixture in which the HFC-32 composition in the HFC-32/HFO-1234yf refrigerant mixture is made to fall within the acceptable range of ±2.0% by weight of the target composition in a container or target equipment until transfer is complete, the upper limit of the HFC-32 composition in the liquid phase of the HFC-32/HFO-1234yf refrigerant mixture immediately prior to transfer is 2.0% by weight of the target composition of HFC-32.

Also, when the mixture contains HFC-32 in an amount of 90% by weight, changes in the composition of HFC-32 are small; therefore, even when the initial composition of HFC-32 is approximately -1.3% by weight of the target composition (90% by weight), the proportion of HFC-32 in the liquid phase of the mixture falls within ±2.0% by weight of the target composition until the transfer is complete.

(1-4) Filling method in which the refrigerant mixture is filled into a container in an amount of 80% by weight of the maximum filling amount

Next, an embodiment is described in which the refrigerant mixture is filled into a container in an amount of 80% by weight of the maximum filling amount of the refrigerant mixture and in which the composition of HFC-32 falls within a range of ±2.0% by weight of the target composition (x) of HFC-32 during the start and finish of the transfer.

In one embodiment of a method of the present invention for filling a refrigerant mixture composed of HFC-32 and HFO-1234yf such that HFC-32 is present in the liquid phase in an amount of 10-90% by weight based on 100 % by weight of the total of HFC-32 and HFO-1234yf, when transferring the refrigerant mixture in a liquid state to a target container or equipment from a feed container that is filled with the refrigerant mixture in an amount < 80% by weight of the maximum filling amount of the refrigerant mixture, the proportion (initial composition) of HFC-32 in the liquid phase of the refrigerant mixture in the feed container is preferably adjusted, before transfer, to x yP ³ % by weight to x 2.0 % by weight, so that the proportion of HFC-32 in the liquid phase of the refrigerant mixture in the feed vessel falls within a range of ±2.0% of a target composition (x) of HFC-32 during startup and completion of the transfer.

(In the above, x is a target composition, provided that 10 < x < 90; and yP3 is a lower bound on a difference between the target composition and the initial composition, and is represented by Equation (19):

1000yP3 = 0.0160X3 - 3.5202x2 1 98.2x - 2382.2 (19) . )

In this embodiment, referring to Equation (19) above, when transferring the refrigerant mixture of HFC-32/HFO-1234yf to a target vessel or equipment from a feed vessel, the proportion of HFC-32 in the liquid phase of the coolant mixture in the feed vessel is adjusted, prior to transfer, to about x - 1.4 wt% to x 2.0 wt%. Changes in composition in a target container or equipment may thus fall within the acceptable range of ±2.0% by weight of the target composition until transfer is complete.

The boiling point of HFC-32 is lower than that of HFO-1234yf. Therefore, when the space created due to refrigerant removal is filled with vapor evaporated from the liquid phase during transfer, e1HFC-32 evaporates in a greater amount than that of HFO-1234yf, causing a reduction in the concentration of HFC-32 in the liquid phase. For this reason, HFC-32 is preferably filled into a feed container before transfer in an amount greater than that of the target composition. In the method for filling a refrigerant mixture in which the HFC-32 composition in the HFC-32/HFO-1234yf refrigerant mixture is made to fall within the acceptable range of ±2.0% by weight of the target composition in a container or target equipment until transfer is complete, the upper limit of the HFC-32 composition in the liquid phase of the HFC-32/HFO-1234yf refrigerant mixture immediately prior to transfer is 2.0% by weight of the target composition of HFC-32.

Also, when the mixture contains HFC-32 in an amount of 90% by weight, changes in the composition of HFC-32 are small; therefore, even when the initial composition of HFC-32 is approximately -1.4% by weight of the target composition (90% by weight), the proportion of HFC-32 in the liquid phase of the mixture falls within ±2.0% by weight of the target composition until the transfer is complete.

(1-5) Filling method in which the refrigerant mixture is filled into a container in an amount of 70% by weight of the maximum filling amount

Next, an embodiment is described in which the refrigerant mixture is filled into a container in an amount of 70% by weight of the maximum filling amount of the refrigerant mixture and in which the composition of HFC-32 falls within a range of ±2.0% by weight of the target composition (x) of HFC-32 during the start and finish of the transfer.

In one embodiment of a method of the present invention for filling a refrigerant mixture composed of HFC-32 and HFO-1234yf such that HFC-32 is present in the liquid phase in an amount of 10-90% by weight based on 100 % by weight of the total of HFC-32 and HFO-1234yf, when transferring the refrigerant mixture in a liquid state to a target container or equipment from a feed container that is filled with the refrigerant mixture in an amount < 70% by weight of the maximum filling quantity of the refrigerant mixture, the proportion (initial composition) of HFC-32 in the liquid phase of the refrigerant mixture in the feed container is preferably adjusted, before transfer, to x yp4 % by weight to x 2.0 % by weight, so that the proportion of HFC-32 in the liquid phase of the refrigerant mixture in the feed vessel falls within a range of ±2.0% of a target composition (x) of HFC-32 during startup and completion of the transfer a.

(In the above, x is a target composition, provided that 10 < x < 90; and yp4 is a lower bound on a difference between the target composition and the initial composition, and is represented by Equation (20):

1000yP4 = 0.0152X3 - 3.3513x2 1 89.76x - 2412.5 (20) . )

In this embodiment, referring to Equation (20) above, when transferring the refrigerant mixture of HFC-32/HFO-1234yf to a target vessel or equipment from a feed vessel, the proportion of HFC-32 in the liquid phase of the coolant mixture in the feed vessel is adjusted, prior to transfer, to about x - 1.4 wt% to x 2.0 wt%. Changes in composition in a target container or equipment may thus fall within the acceptable range of ±2.0% by weight of the target composition until transfer is complete.

The boiling point of HFC-32 is lower than that of HFO-1234yf. Therefore, when the space created due to refrigerant removal is filled with vapor evaporated from the liquid phase during transfer, e1HFC-32 evaporates in a greater amount than that of HFO-1234yf, causing a reduction in the concentration of HFC-32 in the liquid phase. For this reason, HFC-32 is preferably filled into a feed container before transfer in an amount greater than that of the target composition. In the method for filling a refrigerant mixture in which the HFC-32 composition in the HFC-32/HFO-1234yf refrigerant mixture is made to fall within the acceptable range of ±2.0% by weight of the target composition in a container or target equipment until transfer is complete, the upper limit of the HFC-32 composition in the liquid phase of the HFC-32/HFO-1234yf refrigerant mixture immediately prior to transfer is 2.0% by weight of the target composition of HFC-32.

Also, when the mixture contains HFC-32 in an amount of 90% by weight, changes in the composition of HFC-32 are small; therefore, even when the initial composition of HFC-32 is approximately -1.4% by weight of the target composition (90% by weight), the proportion of HFC-32 in the liquid phase of the mixture falls within ±2.0% by weight of the target composition until the transfer is complete.

(1-6) Filling method in which the refrigerant mixture is filled into a container in an amount of 60% by weight of the maximum filling amount

Next, an embodiment is described in which the refrigerant mixture is filled into a container in an amount of 60% by weight of the maximum filling amount of the refrigerant mixture and in which the composition of HFC-32 falls within a range of ±2.0% by weight of the target composition (x) of HFC-32 during the start and finish of the transfer.

In one embodiment of a method of the present invention for filling a refrigerant mixture composed of HFC-32 and HFO-1234yf such that HFC-32 is present in the liquid phase in an amount of 10-90% by weight based on 100 % by weight of the total of HFC-32 and HFO-1234yf, when transferring the refrigerant mixture in a liquid state to a target container or equipment from a feed container that is filled with the refrigerant mixture in an amount < 60% by weight of the maximum filling amount of the refrigerant mixture, the proportion (initial composition) of HFC-32 in the liquid phase of the refrigerant mixture in the feed container is preferably adjusted, before transfer, to x yp5 % by weight to x 2.0 % by weight, so that the proportion of HFC-32 in the liquid phase of the refrigerant mixture in the feed vessel falls within a range of ±2.0% of a target composition (x) of HFC-32 during startup and completion of the transfer a.

(In the above, x is a target composition, provided that 10 < x < 90; and yp5 is a lower bound on a difference between the target composition and the initial composition, and is represented by Equation (21):

1000yP5 = 0.0138X3 - 3.0892x2 176.2x - 2385.7 (21).)

In this embodiment, referring to Equation (21) above, when transferring the refrigerant mixture of HFC-32/HFO-1234yf to a target vessel or equipment from a feed vessel, the proportion of HFC-32 in the liquid phase of the coolant mixture in the feed vessel is adjusted, prior to transfer, to about x - 1.4 wt% to x 2.0 wt%. Changes in composition in a target container or equipment may thus fall within the acceptable range of ±2.0% by weight of the target composition until transfer is complete.

The boiling point of HFC-32 is lower than that of HFO-1234yf. Therefore, when the space created due to refrigerant removal is filled with vapor evaporated from the liquid phase during transfer, e1HFC-32 evaporates in a greater amount than that of HFO-1234yf, causing a reduction in the concentration of HFC-32 in the liquid phase. For this reason, HFC-32 is preferably filled into a feed container before transfer in an amount greater than that of the target composition. In the method for filling a refrigerant mixture in which the HFC-32 composition in the HFC-32/HFO-1234yf refrigerant mixture is made to fall within the acceptable range of ±2.0% by weight of the target composition in a container or target equipment until transfer is complete, the upper limit of the HFC-32 composition in the liquid phase of the HFC-32/HFO-1234yf refrigerant mixture immediately prior to transfer is 2.0% by weight of the target composition of HFC-32.

Also, when the mixture contains HFC-32 in an amount of 90% by weight, changes in the composition of HFC-32 are small; therefore, even when the initial composition of HFC-32 is approximately -1.4% by weight of the target composition (90% by weight), the proportion of HFC-32 in the liquid phase of the mixture falls within ±2.0% by weight of the target composition until the transfer is complete.

(1 -7) Method for filling a non-azeotropic refrigerant mixture composed of HFC-32 and HFO-1234yf

The concept of a filling method of the present invention is shown below, in relation to an embodiment where the HFC-32 composition falls within ±2.0% by weight of the target composition (x) of HFC-32 during the start and end of the transfer.

Equation (16) above can be derived from Equations (17) - (21) above. Based on the value of each coefficient of Equations (17) -(21), L ⁴ to P ⁴ of Equation (16) can be calculated from the target composition (x) with respect to the initial filling amount ( b).

A method of the present invention for filling a mixed refrigerant composed of HFC-32 and HFO-1234yf, the HFC-32 being present in a liquid phase in an amount of 10-90% by weight based on 100% by weight of the total of HFC-32 and HFO-1234yf, it has the following characteristic. Specifically, when transferring the refrigerant mixture in a liquid state to a target container or equipment from a feed container, the proportion (initial composition) of 1HFC-32 in the liquid phase of the refrigerant mixture in the feed container is adjusted immediately before transfer to x and 4 wt% (minimum value) to x 2.0 wt% (maximum value), so that the proportion of 1HFC-32 in the liquid phase of the refrigerant mixture in the feed vessel falls within a set tolerance (±2.0 % by weight) of the target composition (x) of HFC-32 during the start and the end of the transfer. b: an amount (% by weight) initially filled in the feed container;

x: an objective composition, with the condition that 10 < x < 90, which excludes an interval that satisfies the inequality: y4 > 2

y4: a lower bound on the difference between the target composition and the initial composition, y4 which is represented by Equation (16) below:

1000y4 = L4x3 - M4x2 N4x - P4 (16)

L4 = 0.0001b ^0.0081

M4 = ^0.0195b 1.958

N4 = ^0.9878b 118.91

P4 = ^-0.176b 2408.7.

(2) Filling method (established tolerance (±a): ±1.5% by weight)

The mixing ratio is described below in terms of a coolant mixture before it is transferred to a target vessel or equipment from a feed vessel. The use of the blend ratio allows the proportion of HFC-32 in the liquid phase of the refrigerant blend in the feed vessel to fall within a range of ±1.5% by weight of the target composition (x) of HFC-32. 32 during the start and end of the transfer. (2-1) Filling method that allows the composition of HFC-32 to fall within a range of ±1.5% by weight of the target composition (x) of HFC-32

A method (a gas transfer filling method) of the present invention for filling a refrigerant mixture composed of HFC-32 and HFO-1234yf such that HFC-32 is present in the liquid phase in an amount of 10- 90% by weight based on 100% by weight of total HFC-32 and HFO-1234yf, the method of transferring the refrigerant mixture in a liquid state to a target vessel or equipment from a feed vessel that is filled with the refrigerant mixture in an arbitrarily adjusted amount has the following characteristic. Specifically, the proportion (initial composition) of HFC-32 in the liquid phase of the refrigerant mixture in the feed vessel is adjusted immediately before transfer to xy ⁵ % by weight (minimum value) to x 1.5% by weight (maximum value) , so that the proportion of HFC-32 in the liquid phase of the refrigerant mixture in the feed vessel falls within a range of ±1.5% by weight of a target composition (x) of HFC-32 during startup and completion of the transfer.

b: an amount (% by weight) initially filled in the feeding container

x: target composition (provided that 10 < x < 90, which excludes an interval that satisfies an inequality: y5 > ^1.5 )

and ⁵ : a lower bound on the difference between the target composition and the initial composition, and ⁵ which is represented by Equation ( ^{2 2} ) below:

1000y5 = L5x3 - M5x2 N5x - P5 (22)

L5 = ^0.00005b 0.0092

M5 = 0.0171b ^2.1013

N5 = 0.8528b ^125.11

P5 = ^-2.372b 1972.3.

According to the method for filling a refrigerant mixture of the present invention, the proportion of HFC-32 in the liquid phase of the mixture in a feed container is adjusted, before transfer, to a specific range; therefore, even when the feed vessel is filled with the cooling mixture in an amount of ¹⁰⁰ % by weight of the maximum filling amount, the changes in composition in a target vessel or equipment fall within an acceptable range, that is, ±1.5% by weight of the target composition, until the transfer is complete.

The boiling point of HFC-32 is lower than that of HFO-1234yf. Therefore, when the space created due to refrigerant removal is filled with vapor evaporated from the liquid phase during transfer, e1HFC-32 evaporates in a greater amount than that of HFO-1234yf, causing a reduction in the concentration of HFC-32 in the liquid phase. For this reason, HFC-32 is preferably filled into a feed container before transfer in an amount greater than that of the target composition.

The b value above is usually set to 60 < b < 100.

An example is described below with respect to a method that performs transfer at a handling temperature of 40°C. For example, according to Japan's High Pressure Gas Safety Legislation, it is prohibited to handle a container at a temperature of 40°C or higher; therefore, particularly in Japan, the handling temperature is 0-40°C when transferring. A higher temperature during the transfer (at the time of handling) causes a larger compositional change associated with the transfer. Therefore, the conditions for transfer at a handling temperature of 40°C can be applied to the conditions for transfer at a handling temperature of 0-40°C.

Also, with respect to the filling quantity in a feeding container, when the refrigerant mixture in a liquid state is transferred to a target container or equipment from the feeding container, a smaller initial filling quantity results in a composition change. minor associated with the transfer during the start and end of the transfer. Therefore, an equation that satisfies a filling method in which the initial fill amount is b wt% is also satisfied in a filling method in which the initial fill amount is b wt% or less.

(2-2) Filling method in which the refrigerant mixture is filled into a container in an amount of 100% by weight of the maximum filling amount

Next, an embodiment is described in which the refrigerant mixture is filled into a container in an amount of 100% by weight of the maximum filling amount of the refrigerant mixture and in which the composition of HFC-32 falls within a range of ±1.5% by weight of the target composition (x) of HFC-32 during the start and finish of the transfer.

In an embodiment of a method of the present invention for filling a refrigerant mixture composed of HFC-32 and HFO-1234yf such that HFC-32 is present in the liquid phase in an amount of 10-26.5% by weight or 47.5- 90 wt% based on 100 wt% of total HFC-32 and HFO-1234yf, by transferring the refrigerant mixture in a liquid state to a target vessel or equipment from a feed vessel that is filled with the refrigerant mixture in a amount < ^{10 0} % by weight of the maximum filling amount of the refrigerant mixture, the proportion (initial composition) of HFC-32 in the liquid phase of the refrigerant mixture in the feed container is preferably adjusted, before transfer, ax yQ ¹ wt% ax 1.5 wt%, so that the proportion of HFC-32 in the liquid phase of the refrigerant mixture in the feed vessel falls within a range of ±1.5 wt% of a target composition (x ) of HFC-32 during startup and fi completion of the transfer.

(In the above, x is a target composition with the proviso that 10 < x < 26.5 or 47.5 < x <90; and yQ ¹ is a lower bound on a difference between the target composition and the initial composition, and is represented by Equation (23): 1000yQi = 0.0172X3 - 3.75 49 x 2 207.43x - 1705 .9 ( 23 ) . )

In this embodiment, referring to Equation (23) above, when transferring the refrigerant mixture of HFC-32/HFO-1234yf to a target vessel or equipment from a feed vessel, the proportion of HFC-32 in the liquid phase of the coolant mixture in the feed vessel is adjusted, prior to transfer, to about x - 0.9 wt% to x 1.5 wt%. Changes in composition in a target container or equipment may thus fall within the acceptable range of ±1.5% by weight of the target composition until transfer is complete.

The boiling point of HFC-32 is lower than that of HFO-1234yf. Therefore, when the space created due to refrigerant removal is filled with vapor evaporated from the liquid phase during transfer, e1HFC-32 evaporates in a greater amount than that of HFO-1234yf, causing a reduction in the concentration of HFC-32 in the liquid phase. For this reason, HFC-32 is preferably filled into a feed container before transfer in an amount greater than that of the target composition. In the method for filling a refrigerant mixture in which the HFC-32 composition in the HFC-32/HFO-1234yf refrigerant mixture is made to fall within the acceptable range of ±1.5% by weight of the target composition in a container or target equipment until transfer is complete, the upper limit of the HFC-32 composition in the liquid phase of the HFC-32/HFO-1234yf refrigerant mixture immediately prior to transfer is 1.5% by weight of the target composition of HFC-32.

Also, when the mixture contains HFC-32 in an amount of 90% by weight, changes in the composition of HFC-32 are small; therefore, even when the initial composition of HFC-32 is approximately -0.9% by weight of the target composition (90% by weight), the proportion of HFC-32 in the liquid phase of the mixture falls within ±1.5% by weight of the target composition until the transfer is complete.

(2-3) Filling method in which the refrigerant mixture is filled into a container in an amount of 90% by weight of the maximum filling amount

Next, an embodiment is described in which the refrigerant mixture is filled into a container in an amount of 90% by weight of the maximum filling amount of the refrigerant mixture and in which the composition of HFC-32 falls within a range of ±1.5% by weight of the target composition (x) of HFC-32 during the start and finish of the transfer.

In an embodiment of a method of the present invention for filling a refrigerant mixture composed of HFC-32 and HFO-1234yf in such a way that HFC-32 is present in the liquid phase in an amount of 10-30% by weight or 44 -90 wt% based on 100 wt% of total HFC-32 and HFO-1234yf, when transferring the refrigerant mixture in a liquid state to a target vessel or equipment from a feed vessel that is filled with the refrigerant mixture in an amount < 90% by weight of the maximum filling amount of the refrigerant mixture, the proportion (initial composition) of HFC-32 in the liquid phase of the refrigerant mixture in the feed container is preferably adjusted, before transfer, ax yQ ² wt% ax 1.5 wt%, so that the proportion of HFC-32 in the liquid phase of the refrigerant mixture in the feed vessel falls within a range of ±1.5% of a target composition (x) of HFC-32 during startup and completion of the transfer.

(In the above, x is a target composition, provided that 10 < x < 30 or 44 < x <90; and yQ ² is a lower bound on a difference between the target composition and the initial composition, and is represented by Equation (24):

1000yQ2 = 0.0168X3 - 3.6698x2 20 3.75x - 1785.4 (24) . )

In this embodiment, referring to Equation (24) above, when transferring the refrigerant mixture of HFC-32/HFO-1234yf to a target vessel or equipment from a feed vessel, the proportion of HFC-32 in the liquid phase of the coolant mixture in the feed vessel is adjusted, prior to transfer, to about x - 0.9 wt% to x 1.5 wt%. Changes in composition in a target container or equipment may thus fall within the acceptable range of ±1.5% by weight of the target composition until transfer is complete.

The boiling point of HFC-32 is lower than that of HFO-1234yf. Therefore, when the space created due to refrigerant removal is filled with vapor evaporated from the liquid phase during transfer, e1HFC-32 evaporates in a greater amount than that of HFO-1234yf, causing a reduction in the concentration of HFC-32 in the liquid phase. For this reason, HFC-32 is preferably filled into a feed container before transfer in an amount greater than that of the target composition. In the method for filling a refrigerant mixture in which the HFC-32 composition in the HFC-32/HFO-1234yf refrigerant mixture is made to fall within the acceptable range of ±1.5% by weight of the target composition in a container or target equipment until transfer is complete, the upper limit of the HFC-32 composition in the liquid phase of the HFC-32/HFO-1234yf refrigerant mixture immediately prior to transfer is 1.5% by weight of the target composition of HFC-32.

Also, when the mixture contains HFC-32 in an amount of 90% by weight, changes in the composition of HFC-32 are small; therefore, even when the initial composition of HFC-32 is approximately -0.9% by weight of the target composition (90% by weight), the proportion of HFC-32 in the liquid phase of the mixture falls within ±1.5% by weight of the target composition until the transfer is complete.

(2-4) Filling method in which the refrigerant mixture is filled into a container in an amount of 80% by weight of the maximum filling amount

Next, an embodiment is described in which the refrigerant mixture is filled into a container in an amount of 80% by weight of the maximum filling amount of the refrigerant mixture and in which the composition of HFC-32 falls within a range of ±1.5% by weight of the target composition (x) of HFC-32 during the start and finish of the transfer.

In one embodiment of a method of the present invention for filling a refrigerant mixture composed of HFC-32 and HFO-1234yf such that HFC-32 is present in the liquid phase in an amount of 10-90% by weight based on 100 % by weight of the total of HFC-32 and HFO-1234yf, when transferring the refrigerant mixture in a liquid state to a target container or equipment from a feed container that is filled with the refrigerant mixture in an amount < 80% by weight of the maximum filling quantity of the refrigerant mixture, the proportion (initial composition) of HFC-32 in the liquid phase of the refrigerant mixture in the feed container is preferably adjusted, before transfer, to x yQ3 % by weight to x 1.5 % by weight, so that the proportion of HFC-32 in the liquid phase of the refrigerant mixture in the feed vessel falls within a range of ±1.5% by weight of a target composition (x) of HFC-32 during startup and the completion of the transaction sference.

(In the above, x is a target composition, provided that 10 < x < 90; and yQ3 is a lower bound on a difference between the target composition and the initial composition, and is represented by Equation (25):

1000yQ3 = 0.0163X 3 - 3.5445x2 19 7.22x - 1815.9 ( 25 ) . )

In this embodiment, referring to Equation (25) above, when transferring the refrigerant mixture of HFC-32/HFO-1234yf to a target vessel or equipment from a feed vessel, the proportion of HFC-32 in the liquid phase of the coolant mixture in the feed vessel is adjusted, prior to transfer, to about x - 0.9 wt% to x 1.5 wt%. Changes in composition in a target container or equipment may thus fall within the acceptable range of ±1.5% by weight of the target composition until transfer is complete.

The boiling point of HFC-32 is lower than that of HFO-1234yf. Therefore, when the space created due to refrigerant removal is filled with vapor evaporated from the liquid phase during transfer, e1HFC-32 evaporates in a greater amount than that of HFO-1234yf, causing a reduction in the concentration of HFC-32 in the liquid phase. For this reason, HFC-32 is preferably filled into a feed container before transfer in an amount greater than that of the target composition. In the method for filling a refrigerant mixture in which the HFC-32 composition in the HFC-32/HFO-1234yf refrigerant mixture is made to fall within the acceptable range of ±1.5% by weight of the target composition in a container or target equipment until transfer is complete, the upper limit of the HFC-32 composition in the liquid phase of the HFC-32/HFO-1234yf refrigerant mixture immediately prior to transfer is 1.5% by weight of the target composition of HFC-32.

Also, when the mixture contains HFC-32 in an amount of 90% by weight, changes in the composition of HFC-32 are small; therefore, even when the initial composition of HFC-32 is approximately -0.9% by weight of the target composition (90% by weight), the proportion of HFC-32 in the liquid phase of the mixture falls within ±1.5% by weight of the target composition until the transfer is complete.

(2-5) Filling method in which the refrigerant mixture is filled into a container in an amount of 70% by weight of the maximum filling amount

Next, an embodiment is described in which the refrigerant mixture is filled into a container in an amount of 70% by weight of the maximum filling amount of the refrigerant mixture and in which the composition of HFC-32 falls within a range of ±1.5% by weight of the target composition (x) of HFC-32 during the start and finish of the transfer.

In one embodiment of a method of the present invention for filling a refrigerant mixture composed of HFC-32 and HFO-1234yf such that HFC-32 is present in the liquid phase in an amount of 10-90% by weight based on 100 % by weight of the total of HFC-32 and HFO-1234yf, when transferring the refrigerant mixture in a liquid state to a target container or equipment from a feed container that is filled with the refrigerant mixture in an amount < 70% by weight of the maximum filling quantity of the refrigerant mixture, the proportion (initial composition) of HFC-32 in the liquid phase of the refrigerant mixture in the feed container is preferably adjusted, before transfer, to x yQ4 % by weight to x 1.5 % by weight, so that the proportion of HFC-32 in the liquid phase of the refrigerant mixture in the feed vessel is within a range of ±1.5% by weight of a target composition (x) of HFC-32 during start-up and the completion of the trans ference.

(In the above, x is a target composition, provided that 10 < x < 90; and yQ4 is a lower bound on a difference between the target composition and the initial composition, and is represented by Equation (26):

1000yQ4 = 0.0147X3 - 3.2607x2 18 3.21x - 1777.0 (26) . )

In this embodiment, referring to Equation (26) above, when transferring the refrigerant mixture of HFC-32/HFO-1234yf to a target vessel or equipment from a feed vessel, the proportion of HFC-32 in the liquid phase of the coolant mix in the feed vessel is adjusted, prior to transfer, to about x - 0.9 wt% to x 1.5 wt%. Changes in composition in a target container or equipment may thus fall within the acceptable range of ±1.5% by weight of the target composition until transfer is complete.

The boiling point of HFC-32 is lower than that of HFO-1234yf. Therefore, when the space created due to refrigerant removal is filled with vapor evaporated from the liquid phase during transfer, e1HFC-32 evaporates in a greater amount than that of HFO-1234yf, causing a reduction in the concentration of HFC-32 in the liquid phase. For this reason, HFC-32 is preferably filled into a feed container before transfer in an amount greater than that of the target composition. In the method for filling a refrigerant mixture in which the HFC-32 composition in the HFC-32/HFO-1234yf refrigerant mixture is made to fall within the acceptable range of ±1.5% by weight of the target composition in a container or target equipment until transfer is complete, the upper limit of the HFC-32 composition in the liquid phase of the HFC-32/HFO-1234yf refrigerant mixture immediately prior to transfer is 1.5% by weight of the target composition of HFC-32.

Also, when the mixture contains HFC-32 in an amount of 90% by weight, changes in the composition of HFC-32 are small; therefore, even when the initial composition of HFC-32 is approximately -0.9% by weight of the target composition (90% by weight), the proportion of HFC-32 in the liquid phase of the mixture falls within ±1.5% by weight of the target composition until the transfer is complete.

(2-6) Filling method in which the refrigerant mixture is filled into a container in an amount of 60% by weight of the maximum filling amount

Next, an embodiment is described in which the refrigerant mixture is filled into a container in an amount of 60% by weight of the maximum filling amount of the refrigerant mixture and in which the composition of HFC-32 falls within a range of ±1.5% by weight of the target composition (x) of HFC-32 during the start and finish of the transfer.

In one embodiment of a method of the present invention for filling a refrigerant mixture composed of HFC-32 and HFO-1234yf such that HFC-32 is present in the liquid phase in an amount of 10-90% by weight based on 100 % by weight of the total of HFC-32 and HFO-1234yf, when transferring the refrigerant mixture in a liquid state to a target container or equipment from a feed container that is filled with the refrigerant mixture in an amount < 60% by weight of the maximum filling quantity of the refrigerant mixture, the proportion (initial composition) of HFC-32 in the liquid phase of the refrigerant mixture in the feed container is preferably adjusted, before transfer, to x yQ5 % by weight to x 1.5 % by weight, so that the proportion of HFC-32 in the liquid phase of the refrigerant mixture in the feed vessel falls within a range of ±1.5% of a target composition (x) of HFC-32 during startup and completion of the transfer a.

(In the above, x is a target composition, with the proviso that 10 < x < 90; and yQ5 is a lower bound on a difference between the target composition and the initial composition, and is represented by Equation (27):

1000yQ5 = 0.0141X3 - 3.1058X2 1 75.06x - 1828.7 (27) . )

In this embodiment, referring to Equation (27) above, when transferring the refrigerant mixture of HFC-32/HFO-1234yf to a target vessel or equipment from a feed vessel, the proportion of HFC-32 in the liquid phase of the coolant mixture in the feed vessel is adjusted, prior to transfer, to about x - 0.9 wt% to x 1.5 wt%. Changes in composition in a target container or equipment may thus fall within the acceptable range of ±1.5% by weight of the target composition until transfer is complete.

The boiling point of HFC-32 is lower than that of HFO-1234yf. Therefore, when the space created due to refrigerant removal is filled with vapor evaporated from the liquid phase during transfer, e1HFC-32 evaporates in a greater amount than that of HFO-1234yf, causing a reduction in the concentration of HFC-32 in the liquid phase. For this reason, HFC-32 is preferably filled into a feed container before transfer in an amount greater than that of the target composition. In the method for filling a refrigerant mixture in which the HFC-32 composition in the HFC-32/HFO-1234yf refrigerant mixture is made to fall within the acceptable range of ±1.5% by weight of the target composition in a container or target equipment until transfer is complete, the upper limit of the HFC-32 composition in the liquid phase of the HFC-32/HFO-1234yf refrigerant mixture immediately prior to transfer is 1.5% by weight of the target composition of HFC-32.

Also, when the mixture contains HFC-32 in an amount of 90% by weight, changes in the composition of HFC-32 are small; therefore, even when the initial composition of HFC-32 is approximately -0.9% by weight of the target composition (90% by weight), the proportion of HFC-32 in the liquid phase of the mixture falls within ±1.5% by weight of the target composition until the transfer is complete.

(2-7) Method for filling a non-azeotropic refrigerant mixture composed of HFC-32 and HFO-1234yf

The concept of a filling method of the present invention is shown below, in relation to an embodiment where the HFC-32 composition falls within ±1.5% by weight of the target composition (x) of HFC-32 during the start and end of the transfer.

Equation (22) above can be derived from Equations (23) - (27) above. Based on the value of each coefficient of Equations (23)-(27), L ⁵ to P ⁵ of Equation (22) can be calculated from the target composition (x) with respect to the initial fill amount (b).

A method of the present invention for filling a mixed refrigerant composed of HFC-32 and HFO-1234yf, the HFC-32 being present in a liquid phase in an amount of 10-90% by weight based on 100% by weight of the total of HFC-32 and HFO-1234yf, it has the following characteristic. Specifically, when transferring the refrigerant mixture in a liquid state to a target container or equipment from a feed container, the proportion (initial composition) of 1HFC-32 in the liquid phase of the refrigerant mixture in the feed container is adjusted immediately before transfer to x and 5% by weight (minimum value) to x 1.5% by weight (maximum value), so that the proportion of 1HFC-32 in the liquid phase of the refrigerant mixture in the feed container falls within a set tolerance (±1.5 % by weight) of the target composition (x) of HFC-32 during the start and the end of the transfer.

In view of the concept of the present invention described above, when a = 1.5, and the refrigerant mixture is filled into a container in an amount < 100% by weight of the maximum filling amount, if 26.5 < x < 47.5, then i ¹ >1.5; therefore, x is within a range of 10-26.5 wt% or 47.5-90 wt%. Also, when a = 1.5, and the coolant mixture is filled into a container in an amount < 90% of the maximum filling amount, if 30 < x < 44, then yQ ² >1.5; therefore, x is within a range of 10-30 wt% or 44-90 wt%.

b: an amount (% by weight) initially filled in the feeding container;

x: an objective composition, with the condition that 10 < x < 90, which excludes an interval that satisfies the inequality: y5 > 1.5

y5: a lower bound on the difference between the target composition and the initial composition, y5 which is represented by Equation (22) below:

1000y5 = ^{L5X3 - M5X2 +} N5x ^- P5 (22)

L5 = ^0.00005b 0.0092

M5 = 0.0171b ^2.1013

N5 = 0.8528b ^125.11

P5 = ^-2.372b 1972.3.

(3) Filling method (stated tolerance (±a): ±1.0% by weight)

The mixing ratio is described below in terms of a coolant mixture before it is transferred to a target vessel or equipment from a feed vessel. The use of the blend ratio allows the proportion of HFC-32 in the liquid phase of the refrigerant blend in the feed vessel to fall within a range of ±1% by weight of the target composition (x) of HFC-32. 32 during the start and end of the transfer.

(3-1) Filling method that allows the composition of HFC-32 to fall within ±1% by weight of the target composition (x) of HFC-32

A method (a gas transfer filling method) of the present invention for filling a refrigerant mixture composed of HFC-32 and HFO-1234yf such that HFC-32 is present in the liquid phase in an amount of 10- 18.5 wt% or 60-90 wt% based on 100 wt% of total HFC-32 and HFO-1234yf, the method of transferring the refrigerant mixture in a liquid state to a target container or equipment from a feed container which is filled with the coolant mixture in an arbitrarily adjusted amount has the following characteristic. Specifically, the proportion (initial composition) of HFC-32 in the liquid phase of the refrigerant mixture in the feed vessel is adjusted immediately before transfer to x y6 wt% (minimum value) to x 1.0 wt% (maximum value) , so that the proportion of HFC-32 in the liquid phase of the refrigerant mixture in the feed vessel falls within a range of ±1.0% by weight of a target composition (x) of HFC-32 during startup and completion of the transfer.

b: an amount (% by weight) initially filled in the feeding container

x: target composition (provided that 10 < x < 18.5 or 60 < x < 90, which excludes an interval that satisfies an inequality: y6 > 1)

y6: a lower bound on the difference between the target composition and the initial composition, y6 which is represented by Equation (28) below:

1000y6 = L6X3 - M6X2 N6X - P6 (28)

L6 = 0.00009b 0.0086

Me = 0.0183b 2.003

N6 = 0.9237b 117.29

Pe = -1.055b 1292.7.

According to the method for filling a refrigerant mixture of the present invention, the proportion of HFC-32 in the liquid phase of the mixture in a feed container is adjusted, before transfer, to a specific range; therefore, even when the feed vessel is filled with the coolant mixture in an amount of 100% by weight of the maximum filling amount, changes in composition in a target vessel or equipment fall within an acceptable range, i.e. say, ±1.0% by weight of the target composition, until the transfer is complete.

The boiling point of HFC-32 is lower than that of HFO-1234yf. Therefore, when the space created due to refrigerant removal is filled with vapor evaporated from the liquid phase during transfer, e1HFC-32 evaporates in a greater amount than that of HFO-1234yf, causing a reduction in the concentration of HFC-32 in the liquid phase. For this reason, HFC-32 is preferably filled into a feed container before transfer in an amount greater than that of the target composition.

The b value above is usually set to 60 < b < 100.

An example is described below with respect to a method that performs transfer at a handling temperature of 40°C. For example, according to Japan's High Pressure Gas Safety Legislation, it is prohibited to handle a container at a temperature of 40°C or higher; therefore, particularly in Japan, the handling temperature is 0-40°C when transferring. A higher temperature during the transfer (at the time of handling) causes a larger compositional change associated with the transfer. Therefore, the conditions for transfer at a handling temperature of 40°C can be applied to the conditions for transfer at a handling temperature of 0-40°C.

Also, with respect to the filling quantity in a feeding container, when the refrigerant mixture in a liquid state is transferred to a target container or equipment from the feeding container, a smaller initial filling quantity results in a composition change. minor associated with the transfer during the start and end of the transfer. Therefore, an equation that satisfies a filling method in which the initial fill amount is b wt% is also satisfied in a filling method in which the initial fill amount is b wt% or less.

(3-2) Filling method in which the refrigerant mixture is filled into a container in an amount of 100% by weight of the maximum filling amount

Next, an embodiment is described in which the refrigerant mixture is filled into a container in an amount of 100% by weight of the maximum filling amount of the refrigerant mixture and in which the composition of HFC-32 falls within a range of ±1% by weight of the target composition (x) of HFC-32 during the start and finish of the transfer.

In an embodiment of a method of the present invention for filling a refrigerant mixture composed of HFC-32 and HFO-1234yf such that HFC-32 is present in the liquid phase in an amount of 10-13.5% by weight or 67 90 % by weight based on 100% by weight of the total of HFC-32 and HFO-1234yf, when transferring the refrigerant mixture in a liquid state to a target container or equipment from a feed container that is filled with the refrigerant mixture in a quantity < 100% by weight of the maximum filling quantity of the refrigerant mixture, the proportion (initial composition) of HFC-32 in the liquid phase of the refrigerant mixture in the feed container is preferably adjusted, before transfer, to x ym % by weight to x 1.0 % by weight, so that the proportion of HFC-32 in the liquid phase of the refrigerant mixture in the feed vessel falls within a range of ±1.0 % by weight of a target composition (x) of HFCs -32 during start and fi completion of the transfer.

(In the above, x is a target composition, with the proviso that 10 < x < 13.5 or 67 < x < 90; and ym is a lower bound on a difference between the target composition and the initial composition, and is represented by Equation (29):

1000yRi = 0.0178X3 - 3.8363x2 2 09. 59x - 1194.3 (29) . )

In this embodiment, referring to Equation (29) above, when transferring the refrigerant mixture of HFC-32/HFO-1234yf to a target vessel or equipment from a feed vessel, the proportion of HFC-32 in the liquid phase of the coolant mixture in the feed vessel is adjusted, prior to transfer, to about x - 0.4 wt% to x 1.0 wt%. Changes in composition in a target container or equipment may thus fall within the acceptable range of ±1.0% by weight of the target composition until transfer is complete.

The boiling point of HFC-32 is lower than that of HFO-1234yf. Therefore, when the space created due to refrigerant removal is filled with vapor evaporated from the liquid phase during transfer, e1HFC-32 evaporates in a greater amount than that of HFO-1234yf, causing a reduction in the concentration of HFC-32 in the liquid phase. For this reason, HFC-32 is preferably filled into a feed vessel prior to transfer. in an amount greater than that of the target composition. In the method for filling a refrigerant mixture in which the HFC-32 composition in the HFC-32/HFO-1234yf refrigerant mixture is made to fall within the acceptable range of ±1.0% by weight of the target composition in a container or target equipment until transfer is complete, the upper limit of the HFC-32 composition in the liquid phase of the HFC-32/HFO-1234yf refrigerant mixture immediately prior to transfer is 1.0% by weight of the target composition of HFC-32.

Also, when the mixture contains HFC-32 in an amount of 90% by weight, changes in the composition of HFC-32 are small; therefore, even when the initial composition of HFC-32 is approximately -0.4% by weight of the target composition (90% by weight), the proportion of HFC-32 in the liquid phase of the mixture falls within ±1.0% by weight of the target composition until the transfer is complete.

(3-3) Filling method in which the refrigerant mixture is filled into a container in an amount of 90% by weight of the maximum filling amount

Next, an embodiment is described in which the refrigerant mixture is filled into a container in an amount of 90% by weight of the maximum filling amount of the refrigerant mixture and in which the composition of HFC-32 falls within a range of ±1% by weight of the target composition (x) of HFC-32 during the start and finish of the transfer.

In an embodiment of a method of the present invention for filling a refrigerant mixture composed of HFC-32 and HFO-1234yf in such a way that HFC-32 is present in the liquid phase in an amount of 10-14% by weight or 66 -90 wt% based on 100 wt% of total HFC-32 and HFO-1234yf, when transferring the refrigerant mixture in a liquid state to a target vessel or equipment from a feed vessel that is filled with the refrigerant mixture in an amount < 90% by weight of the maximum filling amount of the refrigerant mixture, the proportion (initial composition) of HFC-32 in the liquid phase of the refrigerant mixture in the feed container is preferably adjusted, before transfer, ax yR ² wt% ax 1.0 wt%, so that the proportion of HFC-32 in the liquid phase of the refrigerant mixture in the feed vessel falls within a range of ±1.0 wt% of a target composition (x ) of HFC-32 during the beginning and the end ization of the transfer.

(In the above, x is a target composition, provided that 10 < x < 14 or 66 < x <90; and yR ² is a lower bound on a difference between the target composition and the initial composition, and is represented by Equation (30):

l O O O y ^ = 0.0168X3 - 3.6 386x2 200 .2x - 1192.8 (30) . )

In this embodiment, referring to Equation (30) above, when transferring the refrigerant mixture of HFC-32/HFO-1234yf to a target vessel or equipment from a feed vessel, the proportion of HFC-32 in the liquid phase of the coolant mixture in the feed vessel is adjusted, prior to transfer, to about x - 0.4 wt% to x 1.0 wt%. Changes in composition in a target container or equipment may thus fall within the acceptable range of ±1.0% by weight of the target composition until transfer is complete.

The boiling point of HFC-32 is lower than that of HFO-1234yf. Therefore, when the space created due to refrigerant removal is filled with vapor evaporated from the liquid phase during transfer, e1HFC-32 evaporates in a greater amount than that of HFO-1234yf, causing a reduction in the concentration of HFC-32 in the liquid phase. For this reason, HFC-32 is preferably filled into a feed container before transfer in an amount greater than that of the target composition. In the method for filling a refrigerant mixture in which the HFC-32 composition in the HFC-32/HFO-1234yf refrigerant mixture is made to fall within the acceptable range of ±1.0% by weight of the target composition in a container or target equipment until transfer is complete, the upper limit of the HFC-32 composition in the liquid phase of the HFC-32/HFO-1234yf refrigerant mixture immediately prior to transfer is 1.0% by weight of the target composition of HFC-32.

Also, when the mixture contains HFC-32 in an amount of 90% by weight, changes in the composition of HFC-32 are small; therefore, even when the initial composition of HFC-32 is approximately -0.4% by weight of the target composition (90% by weight), the proportion of HFC-32 in the liquid phase of the mixture falls within ±1.0% by weight of the target composition until the transfer is complete.

(3-4) Filling method in which the refrigerant mixture is filled into a container in an amount of 80% by weight of the maximum filling amount

Next, an embodiment is described in which the refrigerant mixture is filled into a container in an amount of 80% by weight of the maximum filling amount of the refrigerant mixture and in which the composition of HFC-32 falls within a range of ±1% by weight of the target composition (x) of HFC-32 during the start and finish of the transfer.

In an embodiment of a method of the present invention for filling a refrigerant mixture composed of HFC-32 and HFO-1234yf in such a way that HFC-32 is present in the liquid phase in an amount of 10-15.5% by weight or 65 -90 wt% based on 100 wt% of total HFC-32 and HFO-1234yf, when transferring the refrigerant mixture in a liquid state to a target vessel or equipment from a feed vessel that is filled with the refrigerant mixture in an amount < 80% by weight of the maximum filling quantity of the refrigerant mixture, the proportion (initial composition) of HFC-32 in the liquid phase of the refrigerant mixture in the feed vessel is preferably adjusted, prior to transfer, to x yR3 wt% to x 1.0 wt%, so that the proportion of HFC-32 in the liquid phase of the refrigerant mixture in the feed vessel falls within a range of ±1.0% by weight of a target composition (x) of HFC-32 during the start and finish of the transfer.

(In the above, x is a target composition with the proviso that 10 < x < 15.5 or 65 < x < 90; and yR3 is a lower bound on a difference between the target composition and the initial composition, and is represented by Equation (31):

1000yR3 = 0.0159X3 - 3.4616x2 1 91.19x - 1196.0 (31) . )

In this embodiment, referring to Equation (30) above, when transferring the refrigerant mixture of HFC-32/HFO-1234yf to a target vessel or equipment from a feed vessel, the proportion of HFC-32 in the liquid phase of the coolant mixture in the feed vessel is adjusted, prior to transfer, to about x - 0.4 wt% to x 1.0 wt%. Changes in composition in a target container or equipment may thus fall within the acceptable range of ±1.0% by weight of the target composition until transfer is complete.

The boiling point of HFC-32 is lower than that of HFO-1234yf. Therefore, when the space created due to refrigerant removal is filled with vapor evaporated from the liquid phase during transfer, e1HFC-32 evaporates in a greater amount than that of HFO-1234yf, causing a reduction in the concentration of HFC-32 in the liquid phase. For this reason, HFC-32 is preferably filled into a feed container before transfer in an amount greater than that of the target composition. In the method for filling a refrigerant mixture in which the HFC-32 composition in the HFC-32/HFO-1234yf refrigerant mixture is made to fall within the acceptable range of ±1.0% by weight of the target composition in a container or target equipment until transfer is complete, the upper limit of the HFC-32 composition in the liquid phase of the HFC-32/HFO-1234yf refrigerant mixture immediately prior to transfer is 1.0% by weight of the target composition of HFC-32.

Also, when the mixture contains HFC-32 in an amount of 90% by weight, changes in the composition of HFC-32 are small; therefore, even when the initial composition of HFC-32 is approximately -0.4% by weight of the target composition (90% by weight), the proportion of HFC-32 in the liquid phase of the mixture falls within ±1.0% by weight of the target composition until the transfer is complete.

(3-5) Filling method in which the refrigerant mixture is filled into a container in an amount of 70% by weight of the maximum filling amount

Next, an embodiment is described in which the refrigerant mixture is filled into a container in an amount of 70% by weight of the maximum filling amount of the refrigerant mixture and in which the composition of HFC-32 falls within a range of ±1% by weight of the target composition (x) of HFC-32 during the start and finish of the transfer.

In an embodiment of a method of the present invention for filling a refrigerant mixture composed of HFC-32 and HFO-1234yf such that HFC-32 is present in the liquid phase in an amount of 10-16.5% by weight or 62.5- 90 wt% based on 100 wt% of total HFC-32 and HFO-1234yf, by transferring the refrigerant mixture in a liquid state to a target vessel or equipment from a feed vessel that is filled with the refrigerant mixture in a quantity < 70% by weight of the maximum filling quantity of the refrigerant mixture, the proportion (initial composition) of HFC-32 in the liquid phase of the refrigerant mixture in the feed container is preferably adjusted, before transfer, to x yR4 wt% to x 1.0 wt%, so that the proportion of HFC-32 in the liquid phase of the refrigerant mixture in the feed vessel falls within a range of ±1.0 wt% of a target composition (x) of HFC-32 during startup and f completion of the transfer.

(In the above, x is a target composition, with the proviso that 10 < x < 16.5 or 62.5 < x < 90; and yR4 is a lower bound on a difference between the target composition and the initial composition, and is represented by Equation (32):

1000yR4 = 0.015x3 - 3.2938X2 18 2.87x - 1230.1 (32) . )

In this embodiment, referring to Equation (32) above, when transferring the refrigerant mixture of HFC-32/HFO-1234yf to a target vessel or equipment from a feed vessel, the proportion of HFC-32 in the liquid phase of the coolant mixture in the feed vessel is adjusted, prior to transfer, to about x - 0.4 wt% to x 1.0 wt%. Changes in composition in a target container or equipment may thus fall within the acceptable range of ±1.0% by weight of the target composition until transfer is complete.

The boiling point of HFC-32 is lower than that of HFO-1234yf. Therefore, when the space created due to refrigerant removal is filled with vapor evaporated from the liquid phase during transfer, e1HFC-32 evaporates in a greater amount than that of HFO-1234yf, causing a reduction in the concentration of HFC-32 in the liquid phase. For this reason, HFC-32 is preferably filled into a feed container before transfer in an amount greater than that of the target composition. In the method for filling a refrigerant mixture in which the HFC-32 composition in the HFC-32/HFO-1234yf refrigerant mixture is made to fall within the acceptable range of ±1.0% by weight of the target composition in a container or target equipment until transfer is complete, the upper limit of the HFC-32 composition in the liquid phase of the HFC-32/HFO-1234yf blend refrigerant immediately before transfer is 1.0% by weight of the HFC-32 target composition.

Also, when the mixture contains HFC-32 in an amount of 90% by weight, changes in the composition of HFC-32 are small; therefore, even when the initial composition of HFC-32 is approximately -0.4% by weight of the target composition (90% by weight), the proportion of HFC-32 in the liquid phase of the mixture falls within ±1.0% by weight of the target composition until the transfer is complete.

(3-6) Filling method in which the refrigerant mixture is filled into a container in an amount of 60% by weight of the maximum filling amount

Next, an embodiment is described in which the refrigerant mixture is filled into a container in an amount of 60% by weight of the maximum filling amount of the refrigerant mixture and in which the composition of HFC-32 falls within a range of ±1% by weight of the target composition (x) of HFC-32 during the start and finish of the transfer.

In an embodiment of a method of the present invention for filling a refrigerant mixture composed of HFC-32 and HFO-1234yf such that HFC-32 is present in the liquid phase in an amount of 10-18.5% by weight or 60 -90 wt% based on 100 wt% of total HFC-32 and HFO-1234yf, when transferring the refrigerant mixture in a liquid state to a target vessel or equipment from a feed vessel that is filled with the refrigerant mixture in an amount < 60% by weight of the maximum filling amount of the refrigerant mixture, the proportion (initial composition) of HFC-32 in the liquid phase of the refrigerant mixture in the feed container is preferably adjusted, before transfer, a x yR5 wt% a x 1.0 wt%, so that the proportion of HFC-32 in the liquid phase of the refrigerant mixture in the feed vessel falls within a range of ±1.0 wt% of a target composition (x) of HFC-32 during startup and completion of the transfer.

(In the above, x is a target composition, with the proviso that 10 < x < 18.5 or 60 < x < 90; and yR5 is a lower bound on a difference between the target composition and the initial composition, and is represented by Equation (33): 1000yR5 = 0.0141X3 - 3.0949X2 1 72. 07x - 1228.4 (33) . )

In this embodiment, referring to Equation (33) above, when transferring the refrigerant mixture of HFC-32/HFO-1234yf to a target vessel or equipment from a feed vessel, the proportion of HFC-32 in the liquid phase of the coolant mixture in the feed vessel is adjusted, prior to transfer, to about x - 0.5 wt% to x 1.0 wt%. Changes in composition in a target container or equipment may thus fall within the acceptable range of ±1.0% by weight of the target composition until transfer is complete.

The boiling point of HFC-32 is lower than that of HFO-1234yf. Therefore, when the space created due to refrigerant removal is filled with vapor evaporated from the liquid phase during transfer, e1HFC-32 evaporates in a greater amount than that of HFO-1234yf, causing a reduction in the concentration of HFC-32 in the liquid phase. For this reason, HFC-32 is preferably filled into a feed container before transfer in an amount greater than that of the target composition. In the method for filling a refrigerant mixture in which the HFC-32 composition in the HFC-32/HFO-1234yf refrigerant mixture is made to fall within the acceptable range of ±1.0% by weight of the target composition in a container or target equipment until transfer is complete, the upper limit of the HFC-32 composition in the liquid phase of the HFC-32/HFO-1234yf refrigerant mixture immediately prior to transfer is 1.0% by weight of the target composition of HFC-32.

Also, when the mixture contains HFC-32 in an amount of 90% by weight, changes in the composition of HFC-32 are small; therefore, even when the initial composition of HFC-32 is approximately -0.5% by weight of the target composition (90% by weight), the proportion of HFC-32 in the liquid phase of the mixture falls within ±1.0% by weight of the target composition until the transfer is complete.

(3-7) Method for filling a non-azeotropic refrigerant mixture composed of HFC-32 and HFO-1234yf

The concept of a method of filling the present invention is shown below, in relation to an embodiment in which the HFC-32 composition falls within ±1.0% by weight of the target composition (x) of HFC-32 during the transfer start and end.

Equation (28) above can be derived from Equations (29) - (33) above. Based on the value of each coefficient of Equations (29) -(33), U to P6 of Equation (28) can be calculated from the target composition (x) with respect to the initial filling amount (b) .

A method of the present invention for filling a mixed refrigerant composed of HFC-32 and HFO-1234yf, the HFC-32 being present in a liquid phase in an amount of 10-18.5% by weight or 60-90% by weight based on 100% by weight of the total of HFC-32 and HFO-1234yf, has the following characteristic. Specifically, when transferring the refrigerant mixture in a liquid state to a target container or equipment from a feed container, the proportion (initial composition) of HFC-32 in the liquid phase of the refrigerant mixture in the feed container is adjusted immediately before of transfer to x y6% by weight (minimum value) to x 1.0% by weight (maximum value), so that the proportion of HFC-32 in the liquid phase of the refrigerant mixture in the feed container falls within of an established tolerance (±1.0% by weight) of the target composition (x) of HFC-32 during the start and finish of the transfer.

In view of the concept of the present invention described above, when a set tolerance is ±1.0% by weight, and the refrigerant mixture is filled into a container in an amount < 100% by weight of the maximum filling amount, if 13.5 < x < 67, so yR ¹ >1; therefore, x is within a range of 10-13.5 wt% or 67-90 wt%. Also, when a stated tolerance is ±1.0 wt%, and the refrigerant mixture is filled into a container in an amount < 90 wt% of the maximum fill amount, if 14 < x < 66, then yR ² >1; therefore, x is within a range of 10-14 wt% or 66-90 wt%. When a stated tolerance is ±1.0% by weight, and the refrigerant mixture is filled into a container in an amount < 80% by weight of the maximum filling amount, if 15.5 < x < 65, then yR3 >1; therefore, x is within a range of 10-15.5 wt% or 65-90 wt%. When a stated tolerance is ±1.0% by weight, and the refrigerant mixture is filled into a container in an amount equal to or less than 70% by weight of the maximum filling amount, if 16.5 < x < 62.5, then yR4 >1; therefore, x is within a range of 10-16.5 wt% or 62.5-90 wt%. When a stated tolerance is ±1.0 wt%, and the refrigerant mixture is filled into a container in an amount < 60 wt% of the maximum fill amount, if 18.5 < x < 60, then yR5 >1; therefore, x is within a range of 10-18.5 wt% or 60-90 wt%. b: an amount (% by weight) initially filled in the feeding container;

x: an objective composition, with the condition that 10 < x < 18.5 or 60 < x < 90, which excludes an interval that satisfies the inequality: y6 > 1

y6: a lower bound on the difference between the target composition and the initial composition, y6 which is represented by Equation (28) below:

1000y6 = L6x3 - M6x2 N6x - P6 (28)

Le = 0.00009b 0.0086

Me = 0.0183b 2.003

N6 = 0.9237b 117.29

P6 = -1.055b 1292.7.

[3] Application of the method for filling a refrigerant mixture

Among the HFC-32/HFO-1234yf refrigerant mixtures, the object of the present invention is a mixed composition comprising HFC-32 in an amount of 10-90% by weight. However, the idea of the present invention can also be applied to a non-azeotropic mixture comprising HFO-1234yf and any HFC compound having a different boiling point than HFO-1234yf. Examples of a non-azeotropic mixture comprising HFO-1234yf include HFCs such as pentafluoroethane (HfC-125), HFC-152, and HFC-143a; HFOs such as HFO-1234ze(E), HFO-1243zf, and HFO-1225ye; and propane and CO ² .

The feeding container of the present invention is not particularly limited insofar as it is a hermetically sealed container that can store a cooling mixture. Examples thereof include a warehouse, a tank truck and a storage depot. Mix composition is likely to undergo a change when a feed vessel has a small capacity, or when a large amount of a mix is drawn at one time.

In this method, as long as the amount that is initially filled into a feed container is 60-100% by weight of the maximum filling amount, the transfer can be done several times in divided portions until it is complete. This method plays a role even when the transfer stops before the liquid phase is completely transferred.

The equipment to which a refrigerant mixture is transferred can be any device as long as it uses a vapor compression refrigeration cycle. Such a device is not particularly limited, and may be, for example, a refrigeration air conditioning system, a refrigerator, or a hot water supplier.

The vapor compression refrigeration equipment produced by the method of the present invention comprises a refrigerant and the main body of the refrigeration equipment. The main body of the refrigeration equipment is not particularly limited, and a known body of the refrigeration equipment can be used as it is.

To perform the transfer, known means can be used. For example, the transfer can be done using a pressure difference or a pump.

In addition, for example, according to Japan's High Pressure Gas Safety Legislation, it is prohibited to handle a container at a temperature of 40°C or higher; therefore, the handling temperature is essentially 0-40°C when transferring. Also in international legislation, etc., it is required to avoid manipulation high pressure gas at high temperature. A higher temperature during the transfer (at the time of handling) causes a larger compositional change associated with the transfer. Therefore, the conditions for transfer at a handling temperature of 40°C can also be applied to the conditions for transfer at a handling temperature of 0-40°C.

Advantageous effects of the invention

When a non-azeotropic refrigerant mixture composed of 2,3,3,3-tetrafluoropropene and difluoromethane is filled by the method of the present invention, the compositional changes associated with transfer of the refrigerant mixture may fall within an acceptable range.

Description of achievements

The present invention is described with reference to Examples; however, the present invention is not limited thereto, without departing from the scope of the invention.

(1) Reference example 1

A 10 L sealed container was filled with 2,3,3,3-tetrafluoropropene (HFO-1234yf) and difluoromethane (HFC-32) to the maximum amount that could be filled with the composition immediately prior to transfer so that the phase liquid had a fixed composition at 40°C, and the container was kept at 40°C. The maximum filling quantity is defined by legislation and is calculated as follows:

- G = V/C

- G: Mass of fluorocarbon (kg)

- V: Capacity (L) of the container

- C: Constant depending on the type of fluorocarbon

The filling constant C is determined here in Japan as a value obtained by dividing 1.05 by the specific gravity of the gas at 48°C.

When it comes to export, according to international law, the filling constant C is defined as a value obtained by dividing 1.05 by the specific gravity of the gas at 65 °C when passing through tropical regions, and is defined as a value obtained by dividing 1.05 by the specific gravity of the gas at 45 °C when only non-tropical regions are involved.

In Reference Example 1, a value obtained by dividing 1.05 by the specific gravity of the gas at 45 °C or 65 °C was used as the filling constant.

The reasons for selecting 40°C as the temperature during transfer are that the use of vessels at a temperature higher than 40°C is prohibited by Japan's High Pressure Gas Safety Legislation, international laws, etc. they also require avoiding the use of high temperature vessels, and that since a greater compositional change occurs at a higher temperature, data obtained at a temperature of 40°C are assumed to be data from the most severe conditions.

Subsequently, the liquid phase was gradually transferred from the container to another empty container using a pump. Part of the gas was collected through a sampling valve arranged in the middle of a pipe to extract the liquid phase, and the composition of the components was analyzed by gas chromatography.

Tables 1 and 2 show the results of the composition changes during the transfer in Reference Example 1 when the filling amount is calculated using, as the filling constant, the values obtained by dividing 1.05 by the specific gravity of the gas at 45 °C and 65 °C.

45°C

Table 1

65°C

Table 2

As shown in Tables 1 and 2, when the refrigerant mixture is transferred without taking any action, there is a composition difference (composition change) of up to 3-4% by weight with the target composition when all the liquid is removed. before the transfer (at the time of completion of the transfer). Therefore, the expected cooling capacity and cooling capacity (eg, COP) of the target composition cannot be guaranteed during the start and finish of the transfer.

Table 1 shows that the concentration of HFC-32 in the HFC-32/HFO-1234yf refrigerant blend at the time of completion of transfer was lower than that at the time of start of transfer. This is because the boiling point of HFC-32 is lower than the boiling point of HFO-1234yf, and when the space created due to refrigerant removal is filled with vapor evaporated from the liquid phase during transfer, e1HFC- 32 evaporates in an amount greater than that of HFO-1234yf, causing a reduction in the concentration of HFC-32 in the liquid phase. For this reason, it was found that HFC-32 was preferably filled into a feed container before transfer in an amount greater than that of the target composition. Even when the composition change during the transfer was the smallest (HFC-32: 90% by weight), the amplitude of the composition change during the beginning and the end of the transfer was about 0.5% by weight.

(2) Filling method when the filling quantity is 100% by weight of the maximum filling quantity

The filling amount was calculated using a value obtained by dividing 1.05 by the specific gravity of the gas at 65°C as the filling constant.

(2-1) Example 1

Initial composition: 2.5% by weight of the target composition

A 10 L hermetically sealed container was filled with 2,3,3,3-tetrafluoropropene (HFO-1234yf) and difluoromethane (HFC-32) to the maximum amount (100% by weight of the maximum filling amount) that could be filled with the composition immediately before transfer so that the liquid phase had a fixed composition at 40 °C, and the container was maintained at 40 °C. In this case, the initial composition of HFC-32 in the liquid phase before transfer was adjusted to 2.5% by weight of the target composition. Later, as in Example 1 of reference, the liquid phase was gradually transferred from the container to another empty container using a pump, and the composition of the components was analyzed. Table 2 shows the results of composition changes during transfer when the initial composition was adjusted to 2.5% by weight of the target composition.

Table 3

As shown in Table 3, by adjusting the starting composition to 2.5% by weight of the target composition, the difference between the target composition and the starting composition before transfer falls within a range of ±2.5% by weight of the composition. objective when the composition of HFC-32, among the compositions from the start of filling (before transfer) until all liquid is withdrawn (until transfer is complete), is within a range of 10-90% in weight in the refrigerant mixture of HFC-32/HFO-1234yf in the liquid phase.

In addition, the composition of HFC-32 in the HFC-32/HFO-1234yf refrigerant mixture in the liquid phase prior to transfer was determined, which allowed the composition of HFC-32 at the time of completion of transfer outside the -2.5% by weight of the objective composition (x). Table 4 shows the lower limit (yA) of the difference between the target composition and the initial composition in this case.

Table 4

The results show that HFC-32 experiences the least compositional change when the target composition is 90% by weight, and that even when the initial composition of HFC-32 in the HFC-32/HFO-1234yf refrigerant blend in the liquid phase is -1.9% by weight of the target composition, the difference with the target composition falls within a range of ±2.5% by weight of the target composition from before the transfer to the completion of the transfer.

Based on these results, the lower limit (yA) of the difference between the target composition and the initial composition is represented by the following equation using the target composition (x):

1000yA = 0.0166X3 - 3.6757x2 2 08. 97x - 3006.3 (2)

Therefore, when the initial composition of HFC-32 in the refrigerant mixture of HFC-32/HFO-1234yf in the liquid phase is adjusted within a range of yA at 2.5% by weight of the target composition, the difference with the target composition falls within a range of ±2.5% by weight of the target composition from before transfer to completion of transfer.

(2-2) Example 2

Initial composition: 2.0% by weight of the target composition

The analysis was performed as in Example 1, except that the initial composition of HFC-32 in the liquid phase before transfer was adjusted to 2.0% by weight of the target composition. Table 5 shows the results of composition changes during transfer when the initial composition was adjusted to 2.0% by weight of the target composition.

Table 5

As shown in Table 5, by adjusting the starting composition to 2.0% by weight of the target composition, the difference between the target composition and the starting composition before transfer falls within a range of ±2.0% by weight of the composition. objective when the composition of HFC-32, among the compositions from the start of filling (before transfer) until all liquid is withdrawn (until transfer is complete), is within a range of 10-90% in weight in the refrigerant mixture of HFC-32/HFO-1234yf in the liquid phase.

In addition, the composition of HFC-32 in the HFC-32/HFO-1234yf refrigerant blend in the liquid phase prior to transfer was determined which allowed the HFC-32 composition at the time of completion of transfer to be - 2.0% by weight of the objective composition (x). Table 6 shows the lower limit (yB) of the difference between the target composition and the initial composition in this case.

Table 6

The results show that HFC-32 experiences the least compositional change when the target composition is 90% by weight, and that even when the initial composition of HFC-32 in the HFC-32/HFO-1234yf refrigerant blend in the liquid phase is -1.4% by weight of the target composition, the difference with the target composition falls within a range of ±2.0% by weight of the target composition from before the transfer to the completion of the transfer.

Based on these results, the lower bound (yB) of the difference between the target composition and the initial composition is represented by the following equation using the target composition (x):

1000yB = 0.0162X3 - 3.5639x2 + 20 0. 6x - 2347.6 (3)

Therefore, when the initial composition of HFC-32 in the refrigerant mixture of HFC-32/HFO-1234yf in the liquid phase is adjusted within a range of yB at 2.0% by weight of the target composition, the difference with the target composition falls within a range of ±2.0% by weight of the target composition from before transfer to completion of transfer.

(2-3) Example 3

Initial composition: 1.5% by weight of the target composition

The analysis was performed as in Example 1, except that the initial composition of HFC-32 in the liquid phase before transfer was adjusted to 1.5% by weight of the target composition. Table 7 shows the result of composition changes during transfer when the initial composition was adjusted to 1.5% by weight of the target composition.

Table 7

As shown in Table 7, by adjusting the initial composition to 1.5% by weight of the target composition, the difference between the target composition and the initial composition before transfer falls within a range of ±1.5% by weight of the composition. objective when the composition of HFC-32, among the compositions from the beginning of filling (before transfer) until all liquid is withdrawn (until transfer is complete), is within a range of 10-32% in weight or 42-90% by weight in the refrigerant mixture of HFC-32/HFO-1234yf in the liquid phase.

In addition, the composition of HFC-32 in the HFC-32/HFO-1234yf refrigerant blend in the liquid phase prior to transfer was determined which allowed the HFC-32 composition at the time of completion of transfer to be - 1.5% by weight of the objective composition (x). Table 8 shows the lower limit (yC) of the difference between the target composition and the initial composition in this case.

Table 8

The results show that HFC-32 experiences the least compositional change when the target composition is 90% by weight, and that even when the initial composition of HFC-32 in the HFC-32/HFO-1234yf refrigerant blend in the liquid phase is -0.9% by weight of the target composition, the difference with the target composition falls within a range of ±1.5% by weight of the target composition from before the transfer to the completion of the transfer.

Based on these results, the lower limit (ye) of the difference between the target composition and the initial composition is represented by the following equation using the target composition (x):

1000yc = 0.0169X3 - 3.6374x2 199 . 88x-1760.3 (4)

Therefore, when the initial composition of HFC-32 in the refrigerant mixture of HFC-32/HFO-1234yf in the liquid phase is adjusted within a range of yC at 1.5% by weight of the target composition, the difference with the target composition falls within a range of ±1.5% by weight of the target composition from before transfer to completion of transfer.

(2-4) Example 4

Initial composition: 1.0% by weight of the target composition

The analysis was performed as in Example 1, except that the initial composition of HFC-32 in the liquid phase before transfer was adjusted to 1.0% by weight of the target composition. Table 9 shows the result of composition changes during transfer when the initial composition was adjusted to 1.0% by weight of the target composition. Table 9

As shown in Table 9, by adjusting the initial composition to 1.0% by weight of the target composition, the difference between the target composition and the initial composition before transfer falls within a range of ±1.0% by weight of the composition. objective when the composition of HFC-32, among the compositions from the start of filling (before transfer) until all the liquid is withdrawn (until transfer is complete), is within a range of 10-14% in weight or 65-90% by weight in the refrigerant mixture of HFC-32/HFO-1234yf in the liquid phase.

In addition, the composition of HFC-32 in the HFC-32/HFO-1234yf refrigerant blend in the liquid phase prior to transfer was determined which allowed the HFC-32 composition at the time of completion of transfer to be - 1.0% by weight of the objective composition (x). Table 10 shows the lower limit (yD) of the difference between the target composition and the initial composition in this case.

Table 10

The results show that HFC-32 experiences the least compositional change when the target composition is 90% by weight, and that even when the initial composition of HFC-32 in the HFC-32/HFO-1234yf refrigerant blend in the liquid phase is -0.5% by weight of the target composition, the difference with the target composition falls within a range of ±1.5% by weight of the target composition from before the transfer to the completion of the transfer.

Based on these results, the lower limit (yD) of the difference between the target composition and the initial composition is represented by the following equation using the target composition (x):

1000yD = 0.0160X3 - 3.5312x2 19 6. 02x - 1210.8 (5)

Therefore, when the initial composition of HFC-32 in the refrigerant mixture of HFC-32/HFO-1234yf in the liquid phase is adjusted within a range of yD at 1.0% by weight of the target composition, the difference with the target composition falls within a range of ±1.0% by weight of the target composition from before transfer to completion of transfer.

(3) Filling method when the filling amount is 70% by weight of the maximum filling amount

The filling amount was calculated using a value obtained by dividing 1.05 by the specific gravity of the gas at 65°C as the filling constant.

(3-1) Example 5

Initial composition: 2.5% by weight of the target composition

The analysis was performed as in Example 1, except that the initial composition of HFC-32 in the liquid phase before transfer was adjusted to 2.5% by weight of the target composition, and the filling amount was 70% by weight. weight of the maximum amount of filling. Table 11 shows the result of composition changes during transfer when the initial composition was adjusted to 2.5% by weight of the target composition.

Table 11

As shown in Table 11, by setting the starting composition to 2.5% by weight of the target composition, the difference between the target composition and the starting composition before transfer falls within a range of ±2.5% by weight of the composition. objective when the composition of HFC-32, between the compositions from the start of filling (before transfer) until all the liquid is withdrawn (until transfer is complete), is in a range of 10-90% by weight in the refrigerant mixture of HFC-32/HFO-1234yf in the liquid phase.

In addition, the composition of HFC-32 in the HFC-32/HFO-1234yf refrigerant mixture in the liquid phase prior to transfer was determined, which allowed the composition of HFC-32 at the time of completion of transfer outside the -2.5% of target composition (x). Table 12 shows the lower limit (yE) of the difference between the target composition and the initial composition in this case.

Table 12

The results show that HFC-32 experiences the least compositional change when the target composition is 90% by weight, and that even when the initial composition of HFC-32 in the HFC-32/HFO-1234yf refrigerant blend in the liquid phase is -2.0% by weight of the target composition, the difference with the target composition falls within a range of ±2.5% by weight of the target composition from before transfer to completion of transfer.

Based on these results, the lower limit (yE) of the difference between the target composition and the initial composition is represented by the following equation using the target composition (x):

1000yE = 0.013x3 - 3.0285x2 177.93x - 2975.4 (7)

Therefore, when the initial composition of HFC-32 in the refrigerant mixture of HFC-32/HFO-1234yf in the liquid phase is adjusted within a range of yE to 2.5% by weight of the target composition, the difference with the target composition falls within a range of ±2.5% by weight of the target composition from before transfer to completion of transfer.

(3-2) Example 6

Initial composition: 2.0% by weight of the target composition

The analysis was performed as in Example 5, except that the initial composition of HFC-32 in the liquid phase before the transfer was adjusted to 2.0% by weight of the target composition. Table 13 shows the result of the composition changes during the transfer when the initial composition was adjusted to 2.0% by weight of the target composition.

Table 13

As shown in Table 13, by setting the starting composition to 2.0% by weight of the target composition, the difference between the target composition and the starting composition before transfer falls within a range of ±2.0% by weight of the composition. objective when the composition of HFC-32, among the compositions from the start of filling (before transfer) until all liquid is withdrawn (until transfer is complete), is within a range of 10-90% in weight in the refrigerant mixture of HFC-32/HFO-1234yf in the liquid phase.

In addition, the composition of HFC-32 in the HFC-32/HFO-1234yf refrigerant blend in the liquid phase prior to transfer was determined which allowed the HFC-32 composition at the time of completion of transfer to be - 2.0% by weight of the objective composition (x). Table 14 shows the lower limit (yF) of the difference between the target composition and the initial composition in this case.

Table 14

The results show that HFC-32 experiences the least compositional change when the target composition is 90% by weight, and that even when the initial composition of HFC-32 in the HFC-32/HFO-1234yf refrigerant blend in the liquid phase is -1.5% by weight of the target composition, the difference with the target composition falls within a range of ±2.0% by weight of the target composition from before transfer to completion of transfer.

Based on these results, the lower limit (yF) of the difference between the target composition and the initial composition is represented by the following equation using the target composition (x):

1000yF = 0.0132X3 - 2.991x2 17 1.39x - 2327.0 (8)

Therefore, when the initial composition of HFC-32 in the refrigerant mixture of HFC-32/HFO-1234yf in the liquid phase is adjusted within a range of yF at 2.0% by weight of the target composition, the difference with the target composition falls within a range of ±2.0% by weight of the target composition from before transfer to completion of transfer.

(3-3) Example 7

Initial composition: 1.5% by weight of the target composition

The analysis was performed as in Example 5, except that the initial composition of HFC-32 in the liquid phase before transfer was adjusted to 1.5% by weight of the target composition. Table 15 shows the result of composition changes during transfer when the initial composition was adjusted to 1.5% by weight of the target composition.

Table 15

As shown in Table 15, by adjusting the starting composition to 1.5% by weight of the target composition, the difference between the target composition and the starting composition before transfer falls within a range of ±1.5% by weight of the composition. objective when the composition of HFC-32, among the compositions from the start of filling (before transfer) until all liquid is withdrawn (until transfer is complete), is within a range of 10-90% in weight in the refrigerant mixture of HFC-32/HFO-1234yf in the liquid phase.0

In addition, the composition of HFC-32 in the HFC-32/HFO-1234yf refrigerant blend in the liquid phase prior to transfer was determined which allowed the HFC-32 composition at the time of completion of transfer to be - 1.5% by weight of the objective composition (x). Table 16 shows the lower limit (yG) of the difference between the target composition and the initial composition in this case.

Table 16

The results show that HFC-32 experiences the least compositional change when the target composition is 90% by weight, and that even when the initial composition of HFC-32 in the HFC-32/HFO-1234yf refrigerant blend in the liquid phase is -1.0% by weight of the target composition, the difference with the target composition falls within a range of ±1.5% by weight of the target composition from before the transfer to the completion of the transfer.

Based on these results, the lower limit (yG) of the difference between the target composition and the initial composition is represented by the following equation using the target composition (x):

1000yG = 0.0149X3 - 3.2273x2 17 9.57x - 1866.7 (9)

Therefore, when the initial composition of HFC-32 in the refrigerant mixture of HFC-32/HFO-1234yf in the liquid phase is adjusted within a range of yG at 1.5% by weight of the target composition, the difference with the target composition falls within a range of ±1.5% by weight of the target composition from before transfer to completion of transfer.

(3-4) Example 8

Initial composition: 1.0% by weight of the target composition

The analysis was performed as in Example 5, except that the initial composition of HFC-32 in the liquid phase before transfer was adjusted to 1.0% by weight of the target composition. Table 17 shows the result of composition changes during transfer when the initial composition was adjusted to 1.0% by weight of the target composition. Table 17

As shown in Table 17, by setting the starting composition to 1.0% by weight of the target composition, the difference between the target composition and the starting composition before transfer falls within a range of ±1.0% by weight of the composition. objective when the composition of HFC-32, among the compositions from the start of filling (before transfer) until all liquid is withdrawn (until transfer is complete), is within a range of 10-18% in weight or 60-90% by weight in the refrigerant mixture of HFC-32/HFO-1234yf in the liquid phase.

In addition, the composition of HFC-32 in the HFC-32/HFO-1234yf refrigerant blend in the liquid phase prior to transfer was determined which allowed the HFC-32 composition at the time of completion of transfer to be - 1.0% by weight of the objective composition (x). Table 18 shows the lower limit (yH) of the difference between the target composition and the initial composition in this case.

Table 18

The results show that HFC-32 experiences the least compositional change when the target composition is 90% by weight, and that even when the initial composition of HFC-32 in the HFC-32/HFO-1234yf refrigerant blend in the liquid phase is -0.5% by weight of the target composition, the difference with the target composition falls within a range of ±1.5% by weight of the target composition from before the transfer to the completion of the transfer.

Based on these results, the lower limit (yH) of the difference between the target composition and the initial composition is represented by the following equation using the target composition (x):

1000yH = 0.0151X3 - 3.2439X2 + 178 . 32x - 1263.0 (10)

Therefore, when the initial composition of HFC-32 in the refrigerant mixture of HFC-32/HFO-1234yf in the liquid phase is adjusted within a range of yH at 1.0% by weight of the target composition, the difference with the target composition falls within a range of ±1.0% by weight of the target composition from before transfer to completion of transfer.

(4) Filling method when the filling quantity is 100% by weight of the maximum filling quantity

The filling amount was calculated using a value obtained by dividing 1.05 by the specific gravity of the gas at 45°C as the filling constant.

(4-1) Example 9

Initial composition: 2.5% by weight of the target composition

A 10 L hermetically sealed container was filled with 2,3,3,3-tetrafluoropropene (HFO-1234yf) and difluoromethane (HFC-32) to the maximum amount (100% by weight of the maximum filling amount) that could be filled with the composition immediately before transfer so that the liquid phase had a fixed composition at 40 °C, and the container was maintained at 40 °C. In this case, the initial composition of HFC-32 in the liquid phase before transfer was adjusted to 2.5% by weight of the target composition. Subsequently, as in Reference Example 1, the liquid phase was gradually transferred from the container to another empty container using a pump, and the composition of the components was analyzed. Table 2 shows the results of composition changes during transfer when the initial composition was adjusted to 2.5% by weight of the target composition.

Table 19

As shown in Table 19, by setting the initial composition to 2.5% by weight of the target composition, the difference between the target composition and the initial composition before transfer falls within a range of ±2.5% by weight of the composition. objective when the composition of HFC-32, between the compositions from the start from filling (before transfer) until all liquid is withdrawn (until transfer is complete), is within a range of 10-90% by weight in the HFC-32/HFO-1234yf refrigerant blend in the liquid phase. In addition, the composition of HFC-32 in the HFC-32/HFO-1234yf refrigerant mixture in the liquid phase prior to transfer was determined, which allowed the composition of HFC-32 at the time of completion of transfer outside the -2.5% by weight of the objective composition (x). Table 20 shows the lower limit (yi) of the difference between the target composition and the initial composition in this case.

Table 20

The results show that HFC-32 experiences the least compositional change when the target composition is 90% by weight, and that even when the initial composition of HFC-32 in the HFC-32/HFO-1234yf refrigerant blend in the liquid phase is -1.8% by weight of the target composition, the difference with the target composition falls within a range of ±2.5% by weight of the target composition from before the transfer to the completion of the transfer.

Based on these results, the lower limit (yi) of the difference between the target composition and the initial composition is represented by the following equation using the target composition (x):

l O O O y i = 0.0181X3 - 3.9611X2 22 3. l x - 3040.4 (12)

Therefore, when the initial composition of HFC-32 in the refrigerant mixture of HFC-32/HFO-1234yf in the liquid phase is adjusted within a range of yi to 2.5% by weight of the target composition, the difference with the target composition falls within a range of ±2.5% by weight of the target composition from before transfer to completion of transfer.

(4-2) Example 10

Initial composition: 2.0% by weight of the target composition

The analysis was performed as in Example 1, except that the initial composition of HFC-32 in the liquid phase before transfer was adjusted to 2.0% by weight of the target composition. Table 21 shows the results of composition changes during transfer when the initial composition was adjusted to 2.0% by weight of the target composition.

Table 21

As shown in Table 21, by setting the starting composition to 2.0% by weight of the target composition, the difference between the target composition and the starting composition before transfer falls within a range of ±2.0% by weight of the composition. objective when the composition of HFC-32, among the compositions from the start of filling (before transfer) until all liquid is withdrawn (until transfer is complete), is within a range of 10-90% in weight in the refrigerant mixture of HFC-32/HFO-1234yf in the liquid phase.

In addition, the composition of HFC-32 in the HFC-32/HFO-1234yf refrigerant blend in the liquid phase prior to transfer was determined which allowed the HFC-32 composition at the time of completion of transfer to be - 2.0% by weight of the objective composition (x). Table 22 shows the lower limit (yj) of the difference between the target composition and the initial composition in this case.

Table 22

The results show that HFC-32 experiences the least compositional change when the target composition is 90% by weight, and that even when the initial composition of HFC-32 in the HFC-32/HFO-1234yf refrigerant blend in the liquid phase is -1.3% by weight of the target composition, the difference with the target composition falls within a range of ±2.0% by weight of the target composition from before the transfer to the completion of the transfer.

Based on these results, the lower limit (yj) of the difference between the target composition and the initial composition is represented by the following equation using the target composition (x):

1000yj = 0.0177X3 - 3.8614 x 2215.42x - 2373.5 (13)

Therefore, when the initial composition of HFC-32 in the refrigerant mixture of HFC-32/HFO-1234yf in the liquid phase is adjusted within a range of yj at 2.0% by weight of the target composition, the difference with the target composition falls within a range of ±2.0% by weight of the target composition from before transfer to completion of transfer.

(4-3) Example 11

Initial composition: 1.5% by weight of the target composition

The analysis was performed as in Example 1, except that the initial composition of HFC-32 in the liquid phase before transfer was adjusted to 1.5% by weight of the target composition. Table 7 shows the result of composition changes during transfer when the initial composition was adjusted to 1.5% by weight of the target composition.

Table 23

As shown in Table 7, by adjusting the initial composition to 1.5% by weight of the target composition, the difference between the target composition and the initial composition before transfer falls within a range of ±1.5% by weight of the composition. objective when the composition of HFC-32, among the compositions from the start of filling (before transfer) until all liquid is withdrawn (until transfer is complete), is within a range of 10-26.5% in weight or 47.5-90% by weight in the refrigerant mixture of HFC-32/HFO-1234yf in the liquid phase.

In addition, the composition of HFC-32 in the HFC-32/HFO-1234yf refrigerant mixture in the liquid phase prior to transfer was determined, which allowed the composition of HFC-32 at the time of completion of transfer outside the -1.5% by weight of the objective composition (x). Table 24 shows the lower limit (yK of the difference between the target composition and the initial composition in this case.

Table 24

The results show that HFC-32 experiences the least compositional change when the target composition is 90% by weight, and that even when the initial composition of HFC-32 in the HFC-32/HFO-1234yf refrigerant blend in the liquid phase is -0.9% by weight of the target composition, the difference with the target composition falls within a range of ±1.5% by weight of the target composition from before the transfer to the completion of the transfer.

Based on these results, the lower limit (yK) of the difference between the target composition and the initial composition is represented by the following equation using the target composition (x):

1000yK = 0.0172X3 - 3.7549x2 207.43x - 1705.9 (14)

Therefore, when the initial composition of HFC-32 in the refrigerant mixture of HFC-32/HFO-1234yf in the liquid phase is adjusted within a range of yK at 1.5% by weight of the target composition, the difference with the target composition falls within a range of ±1.5% by weight of the target composition from before transfer to completion of transfer.

(4-4) Example 12

Initial composition: 1.0% by weight of the target composition

The analysis was performed as in Example 1, except that the initial composition of HFC-32 in the liquid phase before transfer was adjusted to 1.0% by weight of the target composition. Table 25 shows the result of composition changes during transfer when the initial composition was adjusted to 1.0% by weight of the target composition. Table 25

As shown in Table 25, by setting the initial composition to 1.0% by weight of the target composition, the difference between the target composition and the initial composition before transfer falls within a range of ±1.0% by weight of the composition. objective when the composition of HFC-32, among the compositions from the beginning of filling (before transfer) until all liquid is withdrawn (until transfer is complete), is within a range of 10-13.5% in weight or 67-90% by weight in the refrigerant mixture of HFC-32/HFO-1234yf in the liquid phase.

In addition, the composition of HFC-32 in the HFC-32/HFO-1234yf refrigerant blend in the liquid phase prior to transfer was determined which allowed the HFC-32 composition at the time of completion of transfer to be - 1.0% by weight of the objective composition (x). Table 26 shows the lower limit (yL) of the difference between the target composition and the initial composition in this case.

Table 26

The results show that HFC-32 experiences the least compositional change when the target composition is 90% by weight, and that even when the initial composition of HFC-32 in the HFC-32/HFO-1234yf refrigerant blend in the liquid phase is -0.4% by weight of the target composition, the difference with the target composition falls within a range of ±1.0% by weight of the target composition from before the transfer to the completion of the transfer.

Based on these results, the lower bound (yi_) of the difference between the target composition and the initial composition is represented by the following equation using the target composition (x):

1000yL = 0.0178X3 - 3.8363x2 2 09.59x - 1194.3 (15)

Therefore, when the initial composition of HFC-32 in the refrigerant mixture of HFC-32/HFO-1234yf in the liquid phase is adjusted within a range of yL at 1.0% by weight of the target composition, the difference with the target composition falls within a range of ±1.0% by weight of the target composition from before transfer to completion of transfer.

(5) Reference Example 2

A 10 L sealed container was filled with 2,3,3,3-tetrafluoropropene (HFO-1234yf) and difluoromethane (HFC-32) to the maximum amount that could be filled with the composition immediately prior to transfer so that the phase liquid had a fixed composition at 40°C, and the container was kept at 40°C. The maximum filling amount is calculated as follows:

- G = V/C

- G: Mass of fluorocarbon (kg)

- V: Capacity (L) of the container

- C: Constant depending on the type of fluorocarbon

The filling constant C is determined here in Japan as a value obtained by dividing 1.05 by the specific gravity of the gas at 48°C.

When it comes to export, according to international law, the filling constant C is defined as a value obtained by dividing 1.05 by the specific gravity of the gas at 65 °C when passing through tropical regions, and is defined as a value obtained by dividing 1.05 by the specific gravity of the gas at 45 °C when only non-tropical regions are involved.

In Reference Example 2, a value obtained by dividing 1.05 by the specific gravity of the gas at 45 °C was used as the filling constant.

The reasons for selecting 40 °C as the temperature during transfer are that the use of vessels at a temperature higher than 40 °C is prohibited by Japan's High Pressure Gas Safety Legislation, the Regulations for the Transportation and Storage of Dangerous Goods by Ship, the International Maritime Dangerous Goods Code, etc., and that since a greater compositional change occurs at a higher temperature, it is assumed that the data obtained at a temperature of 40 °C are data from the more severe conditions.

Subsequently, the liquid phase was gradually transferred from the container to another empty container using a pump. Part of the gas was collected through a sampling valve arranged in the middle of a pipe to extract the liquid phase, and the composition of the components was analyzed by gas chromatography.

Table 27 shows the results of composition changes during transfer in Reference Example 2 when the filling amount is calculated using, as the filling constant, a value obtained by dividing 1.05 by the specific gravity of the gas at 45 °C .

45° C (100% by weight of the maximum filling quantity)

Table 27

As shown in Table 27, when the refrigerant mixture is transferred without taking any action, a composition difference (composition change) of up to 3-4% by weight occurs with the target composition when all the liquid is removed before the transfer (at the time of completion of the transfer). Therefore, the expected cooling capacity and refrigerant capacity (eg, COP) of the target composition cannot be guaranteed during the start and finish of the transfer.

Table 27 shows that the concentration of HFC-32 in the HFC-32/HFO-1234yf refrigerant blend at the time of completion of transfer was lower than that at the time of start of transfer. This is because the boiling point of HFC-32 is lower than the boiling point of HFO-1234yf, and when the space created due to refrigerant removal is filled with vapor evaporated from the liquid phase during transfer, the HFC-32 evaporates in an amount greater than that of HFO-1234yf, causing a reduction in the concentration of HFC-32 in the liquid phase. For this reason, it was found that HFC-32 was preferably filled into a feed container before transfer in an amount greater than that of the target composition. Even when the composition change during the transfer was the smallest (HFC-32: 90% by weight), the amplitude of the composition change during the beginning and the end of the transfer was about 0.5% by weight.

(6) Filling method (tolerance: ±2.0)

(6-1) Example 5

Initial fill quantity in the feed container: 100% by weight

A 10 L hermetically sealed container was filled with 2,3,3,3-tetrafluoropropene (HFO-1234yf) and difluoromethane (HFC-32) to the maximum amount (100% by weight of the maximum filling amount) that could be filled with the composition immediately before transfer so that the liquid phase had a fixed composition at 40 °C, and the container was maintained at 40 °C. In this case, the initial composition of HFC-32 in the liquid phase before transfer was adjusted to 2.0% by weight of the target composition. Subsequently, as in Reference Example 2, the liquid phase was gradually transferred from the container to another empty container using a pump, and the composition of the components was analyzed. Table 28 shows the results of composition changes during transfer when the initial composition was adjusted to 2.0% by weight of the target composition.

Table 28

As shown in Table 28, by setting the initial composition to 2.0% by weight of the target composition, the difference between the target composition and the initial composition before transfer falls within a range of ±2.0% by weight of the composition. objective when the composition of HFC-32, among the compositions from the start of filling (before transfer) until all liquid is withdrawn (until transfer is complete), is within a range of 10-90% in weight in the refrigerant mixture of HFC-32/HFO-1234yf in the liquid phase.

In addition, the composition of HFC-32 in the HFC-32/HFO-1234yf refrigerant blend in the liquid phase prior to transfer was determined which allowed the HFC-32 composition at the time of completion of transfer to be - 2% by weight of the objective composition (x). Table 29 shows the lower limit (yP ¹ ) of the difference between the target composition and the initial composition in this case.

Table 29

The results show that HFC-32 experiences the least compositional change when the target composition is 90% by weight, and that even when the initial composition of HFC-32 in the HFC-32/HFO-1234yf refrigerant blend in the liquid phase is -1.3% by weight of the target composition, the difference with the target composition falls within a range of ±2.0% by weight of the target composition from before the transfer to the completion of the transfer.

Based on these results, the lower limit (ypi) of the difference between the target composition and the initial composition is represented by the following equation using the target composition (x):

l O O O and p i = 0.0177X3 - 3.8614x2 215. 42x - 2373.5 (17)

Therefore, when the initial composition of HFC-32 in the refrigerant mixture of HFC-32/HFO-1234yf in the liquid phase is adjusted within a range of ypi at 2% by weight of the target composition, the difference with the target composition falls within a range of ±2.0% by weight of the target composition from before transfer to completion of transfer.

(6-2) Example 14

Initial filling quantity in the feed container: 90% by weight

A 10 L hermetically sealed container was filled with HFO-1234yf and HFC-32 in an amount of 90% by weight of the maximum filling amount that could be filled with the composition immediately before transfer so that the liquid phase had a composition fixed at 40°C, and the container was kept at 40°C. In this case, the initial composition of HFC-32 in the liquid phase before transfer was adjusted to 2.0% by weight of the target composition. Subsequently, as in Example 5, the liquid phase was gradually transferred from the container to another empty container using a pump, and the composition of the components was analyzed. Table 30 shows the results of composition changes during transfer when the initial composition was adjusted to 2.0% by weight of the target composition.

Table 30

As shown in Table 30, by setting the starting composition to 2% by weight of the target composition, the difference between the target composition and the starting composition before transfer falls within a range of ±2.0% by weight of the composition. objective when the composition of HFC-32, among the compositions from the start of filling (before transfer) until all liquid is withdrawn (until transfer is complete), is within a range of 10-90% in weight in the refrigerant mixture of HFC-32/HFO-1234yf in the liquid phase. In addition, the composition of HFC-32 in the HFC-32/HFO-1234yf refrigerant blend in the liquid phase prior to transfer was determined which allowed the HFC-32 composition at the time of completion of transfer to be - 2.0% of target composition (x). Table 31 shows the lower limit (yP ² ) of the difference between the target composition and the initial composition in this case.

Table 31

The results show that HFC-32 experiences the least compositional change when the target composition is 90% by weight, and that even when the initial composition of HFC-32 in the HFC-32/HFO-1234yf refrigerant blend in the liquid phase is -1.3% by weight of the target composition, the difference with the target composition falls within a range of ±2.0% by weight of the target composition from before the transfer to the completion of the transfer.

Based on these results, the lower limit (yp ² ) of the difference between the target composition and the initial composition is represented by the following equation using the target composition (x):

1000yP2 = 0.0172X3 - 3.7532x2 2 10. lx - 2419.3 (18)

Therefore, when the initial composition of HFC-32 in the refrigerant mixture of HFC-32/HFO-1234yf in the liquid phase is adjusted within a range of yP2 at 2.0% by weight of the target composition, the difference with the target composition falls within a range of ±2.0% by weight of the target composition from before transfer to completion of transfer.

(6-3) Example 15

Initial fill quantity in the feed container: 80% by weight

A 10 L hermetically sealed container was filled with HFO-1234yf and HFC-32 in an amount of 80% by weight of the maximum filling amount that could be filled with the composition immediately before transfer so that the liquid phase had a composition fixed at 40 °C, and the container was kept at 40 °C. In this case, the initial composition of HFC-32 in the liquid phase before transfer was adjusted to 2.0% by weight of the target composition. Subsequently, as in Example 5, the liquid phase was gradually transferred from the container to another empty container using a pump and the composition of the components was analyzed. Table 32 shows the results of composition changes during transfer when the initial composition was adjusted to 2.0% by weight of the target composition.

Table 32

As shown in Table 32, by setting the starting composition to 2% by weight of the target composition, the difference between the target composition and the starting composition before transfer falls within a range of ±2% by weight of the composition. objective when the composition of HFC-32, among the compositions from the start of filling (before transfer) until all liquid is withdrawn (until transfer is complete), is within a range of 10-90% in weight in the refrigerant mixture of HFC-32/HFO-1234yf in the liquid phase.

In addition, the composition of HFC-32 in the HFC-32/HFO-1234yf refrigerant blend in the liquid phase prior to transfer was determined which allowed the HFC-32 composition at the time of completion of transfer to be - 2% by weight of the objective composition (x). Table 33 shows the lower limit (yP3) of the difference between the target composition and the initial composition in this case.

Table 33

The results show that HFC-32 experiences the least compositional change when the target composition is 90% by weight, and that even when the initial composition of HFC-32 in the HFC-32/HFO-1234yf refrigerant blend in the liquid phase is -1.4% by weight of the target composition, the difference with the target composition falls within a range of ±2.0% by weight of the target composition from before the transfer to the completion of the transfer.

Based on these results, the lower limit (yp3) of the difference between the target composition and the initial composition is represented by the following equation using the target composition (x):

1000yP3 = 0.016x3 - 3.5202X2 198 .2x - 2382.2 (19)

Therefore, when the initial composition of HFC-32 in the refrigerant mixture of HFC-32/HFO-1234yf in the liquid phase is adjusted within a range of yP3 at 2% by weight of the target composition, the difference with the target composition falls within a range of ±2.0% by weight of the target composition from before transfer to completion of transfer.

(6-4) Example 16

Initial fill quantity in the feed container: 70% by weight

A 10 L sealed container was filled with HFO-1234yf and HFC-32 in an amount of 70% by weight of the maximum fill amount that could be filled with the composition immediately before transfer so that the liquid phase had a composition fixed at 40 °C, and the container was kept at 40 °C. In this case, the initial composition of HFC-32 in the liquid phase before transfer was adjusted to 2.0% by weight of the target composition. Subsequently, as in Example 5, the liquid phase was gradually transferred from the container to another empty container using a pump, and the composition of the components was analyzed. Table 34 shows the results of composition changes during transfer when the initial composition was adjusted to 2.0% by weight of the target composition.

Table 34

As shown in Table 34, by setting the starting composition to 2.0% by weight of the target composition, the difference between the target composition and the starting composition before transfer falls within a range of ±2.0% by weight of the composition. objective when the composition of HFC-32, among the compositions from the start of filling (before transfer) until all liquid is withdrawn (until transfer is complete), is within a range of 10-90% in weight in the refrigerant mixture of HFC-32/HFO-1234yf in the liquid phase. In addition, the composition of HFC-32 in the HFC-32/HFO-1234yf refrigerant blend in the liquid phase prior to transfer was determined which allowed the HFC-32 composition at the time of completion of transfer to be - 2% by weight of the objective composition (x). Table 35 shows the lower limit (yp4) of the difference between the target composition and the initial composition in this case.

Table 35

The results show that HFC-32 experiences the least compositional change when the target composition is 90% by weight, and that even when the initial composition of HFC-32 in the HFC-32/HFO-1234yf refrigerant blend in the liquid phase is -1.4% by weight of the target composition, the difference with the target composition falls within a range of ±2.0% by weight of the target composition from before the transfer to the completion of the transfer.

Based on these results, the lower limit (yp4) of the difference between the target composition and the initial composition is represented by the following equation using the target composition (x):

1000yP4 = 0.0152X3 - 3.3513x2 189.76x - 2412.5 (20)

Therefore, when the initial composition of HFC-32 in the refrigerant mixture of HFC-32/HFO-1234yf in the liquid phase is adjusted within a range of yp4 at 2% by weight of the target composition, the difference with the target composition falls within a range of ±2.0% by weight of the target composition from before transfer to completion of transfer.

(6-5) Example 17

Initial fill quantity in the feed container: 60% by weight

A 10 L hermetically sealed vessel was filled with HFO-1234yf and HFC-32 in an amount of 60% of the maximum fill amount that could be filled with the composition immediately before transfer so that the liquid phase had a fixed composition at 40 °C, and the container was kept at 40 °C. In this case, the initial composition of HFC-32 in the liquid phase before transfer was adjusted to 2.0% by weight of the target composition. Subsequently, as in Example 5, the liquid phase was gradually transferred from the container to another empty container using a pump, and the composition of the components was analyzed. Table 36 shows the results of composition changes during transfer when the initial composition was adjusted to 2.0% by weight of the target composition.

Table 36

As shown in Table 36, by setting the starting composition to 2% by weight of the target composition, the difference between the target composition and the starting composition before transfer falls within a range of ±2.0% by weight of the composition. objective when the composition of HFC-32, among the compositions from the start of filling (before transfer) until all liquid is withdrawn (until transfer is complete), is within a range of 10-90% in weight in the refrigerant mixture of HFC-32/HFO-1234yf in the liquid phase.

In addition, the composition of HFC-32 in the HFC-32/HFO-1234yf refrigerant blend in the liquid phase prior to transfer was determined which allowed the HFC-32 composition at the time of completion of transfer to be - 2% by weight of the objective composition (x). Table 35 shows the lower limit (yP ⁵ ) of the difference between the target composition and the initial composition in this case.

Table 37

The results show that HFC-32 experiences the least compositional change when the target composition is 90% by weight, and that even when the initial composition of HFC-32 in the HFC-32/HFO-1234yf refrigerant blend in the liquid phase is -1.4% by weight of the target composition, the difference with the target composition falls within a range of ±2.0% by weight of the target composition from before the transfer to the completion of the transfer.

Based on these results, the lower limit (yp5) of the difference between the target composition and the initial composition is represented by the following equation using the target composition (x):

1000yP5 = 0.0138X3 - 3.0892x2 176.2x - 2385.7 (21)

Therefore, when the initial composition of HFC-32 in the refrigerant mixture of HFC-32/HFO-1234yf in the liquid phase is adjusted within a range of yp5 at 2% by weight of the target composition, the difference with the target composition falls within a range of ±2.0% by weight of the target composition from before transfer to completion of transfer.

(7) Filling method (tolerance: ±1.5)

(7-1) Example 18

Initial fill quantity in the feed container: 100% by weight

A 10 L hermetically sealed vessel was filled with HFO-1234yf and HFC-32 to the maximum amount (100% of the maximum fill amount) that could be filled with the composition immediately prior to transfer so that the liquid phase had a composition fixed at 40 °C, and the container was kept at 40 °C. In this case, the initial composition of HFC-32 in the liquid phase before transfer was adjusted to 1.5% by weight of the target composition. Subsequently, as in Reference Example 2, the liquid phase was gradually transferred from the container to another empty container using a pump, and the composition of the components was analyzed. Table 38 shows the results of composition changes during transfer when the initial composition was adjusted to 1.5% by weight of the target composition.

Table 38

As shown in Table 38, by adjusting the initial composition to 1.5% by weight of the target composition, the difference between the target composition and the initial composition before transfer falls within a range of ±1.5% by weight of the composition. objective when the composition of HFC-32, among the compositions from the start of filling (before transfer) until all liquid is withdrawn (until transfer is complete), is within a range of 10-26.5% in weight or 47.5-90% by weight in the refrigerant mixture of HFC-32/HFO-1234yf in the liquid phase.

In addition, the composition of HFC-32 in the HFC-32/HFO-1234yf refrigerant mixture in the liquid phase prior to transfer was determined, which allowed the composition of HFC-32 at the time of completion of transfer outside the -1.5% by weight of the objective composition (x). Table 39 shows the lower limit (yQ ¹ ) of the difference between the target composition and the initial composition in this case.

Table 39

The results show that HFC-32 experiences the least compositional change when the target composition is 90% by weight, and that even when the initial composition of HFC-32 in the HFC-32/HFO-1234yf refrigerant blend in the liquid phase is -0.9% by weight of the target composition, the difference with the target composition falls within a range of ±1.5% by weight of the target composition from before the transfer to the completion of the transfer.

Based on these results, the lower limit (yQ ¹ ) of the difference between the target composition and the initial composition is represented by the following equation using the target composition (x):

1000yQi = 0.0172X3 - 3.7549x2 2 07. 43x - 1705.9 (23)

Therefore, when the initial composition of HFC-32 in the refrigerant mixture of HFC-32/HFO-1234yf in the liquid phase is adjusted within a range of yQ ¹ to 1.5% by weight of the target composition, the difference with the target composition falls within a range of ±1.5% by weight of the target composition from before transfer to completion of transfer.

(7-2) Example 19

Initial fill quantity in the feed container: 90% by weight

A 10 L hermetically sealed container was filled with HFO-1234yf and HFC-32 in an amount of 90% of the maximum filling amount that could be filled with the composition immediately before transfer so that the liquid phase had a fixed composition at 40 °C, and the container was kept at 40 °C. In this case, the initial composition of HFC-32 in the liquid phase before transfer was adjusted to 1.5% by weight of the target composition. Subsequently, as in Example 10, the liquid phase was gradually transferred from the container to another empty container using a pump, and the composition of the components was analyzed. Table 40 shows the results of composition changes during transfer when the initial composition was adjusted to 1.5% by weight of the target composition.

Table 40

As shown in Table 40, by adjusting the starting composition to 1.5% by weight of the target composition, the difference between the target composition and the starting composition before transfer falls within a range of ±1.5% by weight of the composition. objective when the composition of HFC-32, among the compositions from the start of filling (before transfer) until all liquid is withdrawn (until transfer is complete), is within a range of 10-30% in weight or 44-90% by weight in the refrigerant mixture of HFC-32/HFO-1234yf in the liquid phase.

In addition, the composition of HFC-32 in the HFC-32/HFO-1234yf refrigerant mixture in the liquid phase prior to transfer was determined, which allowed the composition of HFC-32 at the time of completion of transfer outside the -1.5% by weight of the objective composition (x). Table 41 shows the lower limit (yQ ² ) of the difference between the target composition and the initial composition in this case.

Table 41

The results show that HFC-32 experiences the least compositional change when the target composition is 90% by weight, and that even when the initial composition of HFC-32 in the HFC-32/HFO-1234yf refrigerant blend in the liquid phase is -0.9% by weight of the target composition, the difference with the target composition falls within a range of ±1.5% by weight of the target composition from before the transfer to the completion of the transfer.

Based on these results, the lower limit (yQ ² ) of the difference between the target composition and the initial composition is represented by the following equation using the target composition (x):

1000yQ2 = 0.0168X3 - 3.6698x2 2 03. 75x - 1785.4 (24)

Therefore, when the initial composition of HFC-32 in the refrigerant mixture of HFC-32/HFO-1234yf in the liquid phase is adjusted within a range of yQ2 at 1.5% by weight of the target composition, the difference with the target composition falls within a range of ±1.5% by weight of the target composition from before transfer to completion of transfer.

(7-3) Example 20

Initial fill quantity in the feed container: 80% by weight

A 10 L hermetically sealed vessel was filled with HFO-1234yf and HFC-32 in an amount of 80% of the maximum fill amount that could be filled with the composition immediately before transfer so that the liquid phase had a fixed composition at 40 °C, and the container was kept at 40 °C. In this case, the initial composition of HFC-32 in the liquid phase before transfer was adjusted to 1.5% by weight of the target composition. Subsequently, as in Example 10, the liquid phase was gradually transferred from the container to another empty container using a pump, and the composition of the components was analyzed. Table 42 shows the results of composition changes during transfer when the initial composition was adjusted to 1.5% by weight of the target composition.

Table 42

As shown in Table 42, by adjusting the initial composition to 1.5% by weight of the target composition, the difference between the target composition and the initial composition before transfer falls within a range of ±1.5% by weight of the composition. objective when the composition of HFC-32, among the compositions from the start of filling (before transfer) until all liquid is withdrawn (until transfer is complete), is within a range of 10-90% in weight in the refrigerant mixture of HFC-32/HFO-1234yf in the liquid phase.

In addition, the composition of HFC-32 in the HFC-32/HFO-1234yf refrigerant blend in the liquid phase prior to transfer was determined which allowed the HFC-32 composition at the time of completion of transfer to be - 1.5% by weight of the objective composition (x). Table 43 shows the lower limit (yQ3) of the difference between the target composition and the initial composition in this case.

Table 43

The results show that HFC-32 experiences the least compositional change when the target composition is 90% by weight, and that even when the initial composition of HFC-32 in the HFC-32/HFO-1234yf refrigerant blend in the liquid phase is -0.9% by weight of the target composition, the difference with the target composition falls within a range of ±1.5% by weight of the target composition from before the transfer to the completion of the transfer.

Based on these results, the lower limit (yQ3) of the difference between the target composition and the initial composition is represented by the following equation using the target composition (x):

1000yQ3 = 0.0163X3 - 3.5445x2 1 97.22x - 1815.9 (25)

Therefore, when the initial composition of HFC-32 in the refrigerant mixture of HFC-32/HFO-1234yf in the liquid phase is adjusted within a range of yQ3 at 1.5% by weight of the target composition, the difference with the target composition falls within a range of ±1.5% by weight of the target composition from before transfer to completion of transfer.

(7-4) Example 21

Initial fill quantity in the feed container: 70% by weight

A 10 L hermetically sealed container was filled with HFO-1234yf and HFC-32 in an amount of 70% of the maximum filling amount that could be filled with the composition immediately before transfer so that the liquid phase had a fixed composition. at 40 °C, and the container was kept at 40 °C. In this case, the initial composition of HFC-32 in the liquid phase before transfer was adjusted to 1.5% by weight of the target composition. Subsequently, as in Example 10, the liquid phase was gradually transferred from the container to another empty container using a pump, and the composition of the components was analyzed. Table 44 shows the results of composition changes during transfer when the initial composition was adjusted to 1.5% by weight of the target composition.

Table 44

As shown in Table 44, by adjusting the starting composition to 1.5% by weight of the target composition, the difference between the target composition and the starting composition before transfer falls within a range of ±1.5% by weight of the composition. objective when the composition of HFC-32, among the compositions from the start of filling (before transfer) until all liquid is withdrawn (until transfer is complete), is within a range of 10-90% in weight in the refrigerant mixture of HFC-32/HFO-1234yf in the liquid phase. In addition, the composition of HFC-32 in the HFC-32/HFO-1234yf refrigerant blend in the liquid phase prior to transfer was determined which allowed the HFC-32 composition at the time of completion of transfer to be - 1.5% by weight of the target composition (x). Table 45 shows the lower limit (yQ4) of the difference between the target composition and the initial composition in this case.

Table 45

The results show that HFC-32 experiences the least compositional change when the target composition is 90% by weight, and that even when the initial composition of HFC-32 in the HFC-32/HFO-1234yf refrigerant blend in the liquid phase is -0.9% by weight of the target composition, the difference with the target composition falls within a range of ±1.5% by weight of the target composition from before the transfer to the completion of the transfer.

Based on these results, the lower limit (yQ4) of the difference between the target composition and the initial composition is represented by the following equation using the target composition (x):

1000yQ4 = 0.0147X3 - 3.2607x2 1 83.21x - 1777.0 (26)

Therefore, when the initial composition of HFC-32 in the refrigerant mixture of HFC-32/HFO-1234yf in the liquid phase is adjusted within a range of yQ4 at 1.5% by weight of the target composition, the difference with the target composition falls within a range of ±1.5% by weight of the target composition from before transfer to completion of transfer.

(7-5) Example 22

Initial fill quantity in the feed container: 60% by weight

A 10 L hermetically sealed vessel was filled with HFO-1234yf and HFC-32 in an amount of 60% of the maximum fill amount that could be filled with the composition immediately before transfer so that the liquid phase had a fixed composition at 40 °C, and the container was kept at 40 °C. In this case, the initial composition of HFC-32 in the liquid phase before transfer was adjusted to 1.5% by weight of the target composition. Subsequently, as in Example 10, the liquid phase was gradually transferred from the container to another empty container. using a pump, and the composition of the components was analyzed. Table 46 shows the results of composition changes during transfer when the initial composition was adjusted to 1.5% by weight of the target composition.

Table 46

As shown in Table 46, by adjusting the starting composition to 1.5% by weight of the target composition, the difference between the target composition and the starting composition before transfer falls within a range of ±1.5% by weight of the composition. objective when the composition of HFC-32, among the compositions from the start of filling (before transfer) until all liquid is withdrawn (until transfer is complete), is within a range of 10-90% in weight in the refrigerant mixture of HFC-32/HFO-1234yf in the liquid phase.

In addition, the composition of HFC-32 in the HFC-32/HFO-1234yf refrigerant blend in the liquid phase prior to transfer was determined which allowed the HFC-32 composition at the time of completion of transfer to be - 1.5% by weight of the objective composition (x). Table 47 shows the lower limit (yQ5) of the difference between the target composition and the initial composition in this case.

Table 47

The results show that HFC-32 experiences the least compositional change when the target composition is 90% by weight, and that even when the initial composition of HFC-32 in the HFC-32/HFO-1234yf refrigerant blend in the liquid phase is -0.9% by weight of the target composition, the difference with the target composition falls within a range of ±1.5% by weight of the target composition from before the transfer to the completion of the transfer.

Based on these results, the lower limit (yQ5) of the difference between the target composition and the initial composition is represented by the following equation using the target composition (x):

1000yQ5 = 0.0141X3 - 3.1058X2 175 .06x - 1828.7 (27)

Therefore, when the initial composition of HFC-32 in the refrigerant mixture of HFC-32/HFO-1234yf in the liquid phase is adjusted within a range of yQ5 at 1.5% by weight of the target composition, the difference with the target composition falls within a range of ±1.5% by weight of the target composition from before transfer to completion of transfer.

(8) Filling method (tolerance: ±1.0)

(8-1) Example 23

Initial fill quantity in the feed container: 100% by weight

A 10 L hermetically sealed vessel was filled with HFO-1234yf and HFC-32 to the maximum amount (100% of the maximum fill amount) that could be filled with the composition immediately prior to transfer so that the liquid phase had a composition fixed at 40 °C, and the container was kept at 40 °C. In this case, the initial composition of HFC-32 in the liquid phase before transfer was adjusted to 1% by weight of the target composition. Subsequently, as in Reference Example 2, the liquid phase was gradually transferred from the container to another empty container using a pump, and the composition of the components was analyzed. Table 48 shows the results of the composition changes during the transfer when the initial composition was adjusted to 1.0% by weight of the target composition.

Table 48

As shown in Table 48, by setting the initial composition to 1.0% by weight of the target composition, the difference between the target composition and the initial composition before transfer falls within a range of ±1.0% by weight of the composition. objective when the composition of HFC-32, among the compositions from the beginning of filling (before transfer) until all liquid is withdrawn (until transfer is complete), is within a range of 10-13.5% in weight or 67-90% by weight in the refrigerant mixture of HFC-32/HFO-1234yf in the liquid phase.

In addition, the composition of HFC-32 in the HFC-32/HFO-1234yf refrigerant blend in the liquid phase prior to transfer was determined which allowed the HFC-32 composition at the time of completion of transfer to be - 1% by weight of the objective composition (x). Table 49 shows the lower limit (ym) of the difference between the target composition and the initial composition in this case.

Table 49

The results show that HFC-32 experiences the least compositional change when the target composition is 90% by weight, and that even when the initial composition of HFC-32 in the HFC-32/HFO-1234yf refrigerant blend in the liquid phase is -0.4% by weight of the target composition, the difference with the target composition falls within a range of ±1.0% by weight of the target composition from before the transfer to the completion of the transfer.

Based on these results, the lower limit (ym) of the difference between the target composition and the initial composition is represented by the following equation using the target composition (x):

1000yRi = 0.0178x3 - 3.8363x2 2 09. 59x - 1194.3 (29)

Therefore, when the initial composition of HFC-32 in the refrigerant mixture of HFC-32/HFO-1234yf in the liquid phase is adjusted within a range of ym at 1% by weight of the target composition, the difference with the target composition falls within a range of ±1.0% by weight of the target composition from before transfer to completion of transfer.

(8-2) Example 24

Initial fill quantity in the feed container: 90% by weight

A 10 L hermetically sealed vessel was filled with HFO-1234yf and HFC-32 in an amount of 90% of the maximum fill amount that could be filled with the composition immediately before transfer so that the liquid phase had a fixed composition at 40 °C, and the container was kept at 40 °C. In this case, the initial composition of HFC-32 in the liquid phase before transfer was adjusted to 1.0% by weight of the target composition. Subsequently, as in Example 15, the liquid phase was gradually transferred from the container to another empty container using a pump, and the composition of the components was analyzed. Table 50 shows the results of composition changes during transfer when the initial composition was adjusted to 1.0% by weight of the target composition.

Table 50

As shown in Table 50, by setting the initial composition to 1.0% by weight of the target composition, the difference between the target composition and the initial composition before transfer falls within a range of ±1.0% by weight of the composition. objective when the composition of HFC-32, among the compositions from the start of filling (before transfer) until all the liquid is withdrawn (until transfer is complete), is within a range of 10-14% in weight or 66-90% by weight in the refrigerant mixture of HFC-32/HFO-1234yf in the liquid phase.

In addition, the composition of HFC-32 in the HFC-32/HFO-1234yf refrigerant blend in the liquid phase prior to transfer was determined which allowed the HFC-32 composition at the time of completion of transfer to be - 1% by weight of the objective composition (x). Table 51 shows the lower limit (yR ² ) of the difference between the target composition and the initial composition in this case.

Table 51

The results show that HFC-32 experiences the least compositional change when the target composition is 90% by weight, and that even when the initial composition of HFC-32 in the HFC-32/HFO-1234yf refrigerant blend in the liquid phase is -0.4% by weight of the target composition, the difference with the target composition falls within a range of ±1.0% by weight of the target composition from before the transfer to the completion of the transfer.

Based on these results, the lower limit (yra) of the difference between the target composition and the initial composition is represented by the following equation using the target composition (x):

1000YR2 = 0.0168X3 - 3.638 6x2 200.2x - 1192 .8 (30)

Therefore, when the initial composition of HFC-32 in the refrigerant mixture of HFC-32/HFO-1234yf in the liquid phase is adjusted within a range of yR ² at 1% by weight of the target composition, the difference with the target composition falls within a range of ±1.0% by weight of the target composition from before transfer to completion of transfer.

(8-3) Example 25

Initial fill quantity in the feed container: 80% by weight

A 10 L hermetically sealed container was filled with HFO-1234yf and HFC-32 in an amount of 80% by weight of the maximum filling amount that could be filled with the composition immediately before transfer so that the liquid phase had a composition fixed at 40 °C, and the container was kept at 40 °C. In this case, the initial composition of HFC-32 in the liquid phase before transfer was adjusted to 1.0% by weight of the target composition. Subsequently, as in Example 15, the liquid phase was gradually transferred from the container to another empty container using a pump, and the composition of the components was analyzed. Table 52 shows the results of the composition changes during the transfer when the initial composition was adjusted to 1.0% by weight of the target composition.

Table 52

As shown in Table 52, by setting the starting composition to 1.0% by weight of the target composition, the difference between the target composition and the starting composition before transfer falls within a range of ±1.0% by weight of the composition. objective when the composition of HFC-32, among the compositions from the beginning of filling (before transfer) until all liquid is withdrawn (until transfer is complete), is within a range of 10-15.5% in weight or 65-90% by weight in the refrigerant mixture of HFC-32/HFO-1234yf in the liquid phase.

In addition, the composition of HFC-32 in the HFC-32/HFO-1234yf refrigerant blend in the liquid phase prior to transfer was determined which allowed the HFC-32 composition at the time of completion of transfer to be - 1% by weight of the objective composition (x). Table 53 shows the lower limit (yR3) of the difference between the target composition and the initial composition in this case.

Table 53

The results show that HFC-32 experiences the least compositional change when the target composition is 90% by weight, and that even when the initial composition of HFC-32 in the HFC-32/HFO-1234yf refrigerant blend in the liquid phase is -0.4% by weight of the target composition, the difference with the target composition falls within a range of ±1.0% by weight of the target composition from before the transfer to the completion of the transfer.

Based on these results, the lower limit (yR3) of the difference between the target composition and the initial composition is represented by the following equation using the target composition (x):

1000yR3 = 0.0159X3 - 3.4616x2 191.19x - 1196.0 (31)

Therefore, when the initial composition of HFC-32 in the refrigerant mixture of HFC-32/HFO-1234yf in the liquid phase is adjusted within a range of yR3 at 1% by weight of the target composition, the difference with the target composition falls within a range of ±1.0% by weight of the target composition from before transfer to completion of transfer.

(8-4) Example 26

Initial fill quantity in the feed container: 70% by weight

A 10 L sealed container was filled with HFO-1234yf and HFC-32 in an amount of 70% by weight of the maximum fill amount that could be filled with the composition immediately before transfer so that the liquid phase had a composition fixed at 40 °C, and the container was kept at 40 °C. In this case, the initial composition of HFC-32 in the liquid phase before transfer was adjusted to 1.0% by weight of the target composition. Subsequently, as in Example 15, the liquid phase was gradually transferred from the container to another empty container using a pump, and the composition of the components was analyzed. Table 54 shows the results of the composition changes during the transfer when the initial composition was adjusted to 1.0% by weight of the target composition.

Table 54

As shown in Table 54, by adjusting the initial composition to 1.0% by weight of the target composition, the difference between the target composition and the initial composition before transfer falls within a range of ±1.0% by weight of the target composition when the HFC-32 composition, between the compositions from the start of filling (before transfer) until all liquid is withdrawn (until transfer is complete), is within a range of 10-16.5% by weight or 62.5-90% by weight in the refrigerant mixture of HFC-32/HFO-1234yf in the liquid phase.

In addition, the composition of HFC-32 in the HFC-32/HFO-1234yf refrigerant blend in the liquid phase prior to transfer was determined which allowed the HFC-32 composition at the time of completion of transfer to be - 1% by weight of the objective composition (x). Table 55 shows the lower limit (yR4) of the difference between the target composition and the initial composition in this case.

Table 55

The results show that HFC-32 experiences the least compositional change when the target composition is 90% by weight, and that even when the initial composition of HFC-32 in the HFC-32/HFO-1234yf refrigerant blend in the liquid phase is -0.4% by weight of the target composition, the difference with the target composition falls within a range of ±1.0% by weight of the target composition from before the transfer to the completion of the transfer.

Based on these results, the lower limit (yR4) of the difference between the target composition and the initial composition is represented by the following equation using the target composition (x):

1000yR4 = 0.015x3 - 3.2938X2 182 . 87x - 1230.1 (32)

Therefore, when the initial composition of HFC-32 in the refrigerant mixture of HFC-32/HFO-1234yf in the liquid phase is adjusted within a range of yR4 at 1% by weight of the target composition, the difference with the target composition falls within a range of ±1.0% by weight of the target composition from before transfer to completion of transfer.

(8-5) Example 27

Initial fill quantity in the feed container: 60% by weight

A 10 L sealed container was filled with HFO-1234yf and HFC-32 in an amount of 60% by weight of the maximum fill amount that could be filled with the composition immediately before transfer so that the liquid phase had a composition fixed at 40°C, and the container was kept at 40°C. In this case, the initial composition of HFC-32 in the liquid phase before transfer was adjusted to 1.0% by weight of the target composition. Subsequently, as in Example 15, the liquid phase was gradually transferred from the container to another empty container using a pump, and the composition of the components was analyzed. Table 56 shows the results of the composition changes during the transfer when the initial composition was adjusted to 1.0% by weight of the target composition.

Table 56

As shown in Table 56, by setting the initial composition to 1.0% by weight of the target composition, the difference between the target composition and the initial composition before transfer falls within a range of ±1.0% by weight of the composition. objective when the composition of HFC-32, among the compositions from the beginning of filling (before transfer) until all liquid is withdrawn (until transfer is complete), is within a range of 10-18.5% in weight or 60-90% by weight in the refrigerant mixture of HFC-32/HFO-1234yf in the liquid phase.

In addition, the composition of HFC-32 in the HFC-32/HFO-1234yf refrigerant blend in the liquid phase prior to transfer was determined which allowed the HFC-32 composition at the time of completion of transfer to be - 1% by weight of the objective composition (x). Table 57 shows the lower limit (yR5) of the difference between the target composition and the initial composition in this case.

Table 57

The results show that HFC-32 experiences the least compositional change when the target composition is 90% by weight, and that even when the initial composition of HFC-32 in the HFC-32/HFO-1234yf refrigerant blend in the liquid phase is -0.5% by weight of the target composition, the difference with the target composition falls within a range of ±1.0% by weight of the target composition from before the transfer to the completion of the transfer.

Based on these results, the lower limit (yR5) of the difference between the target composition and the initial composition is represented by the following equation using the target composition (x):

1000yR5 = 0.0141X3 - 3.0949X2 172.07x - 1228.4 (33)

Therefore, when the initial composition of HFC-32 in the refrigerant mixture of HFC-32/HFO-1234yf in the liquid phase is adjusted within a range of yR5 at 1% by weight of the target composition, the difference with the target composition falls within a range of ±1.0% by weight of the target composition from before transfer to completion of transfer.

(5) Discussion

As is apparent from the results of the above Examples, the present invention provides a novel method of filling a non-azeotropic refrigerant mixture that allows the composition changes associated with the transfer of the refrigerant mixture to fall within a fixed range of the target composition. from before the transfer until the end of the transfer, compared to when the refrigerant mixture is transferred without taking any action, and that also allows the use of the entire amount of the liquid phase.

The realization of the method of the present invention leads to a significant result in which the composition changes that occur during the transfer of a non-azeotropic HFO-1234yf/HFC-32 refrigerant mixture, which is used as a working medium for a cycle vapor compression refrigeration, fall within a range that does not impair the cooling capacity.

Claims (7)

1. A method for filling a refrigerant mixture composed of difluoromethane (HFC-32) and 2,3,3,3-tetrafluoropropene (HFO-1234yf), HFC-32 being present in the liquid phase in an amount of 10-90% by weight based on 100% by weight of total HFC-32 and HFO-1234yf, the method comprising, by transferring the refrigerant mixture in a liquid state to a target container or equipment from a feed container, adjust, immediately before transfer, the proportion (initial composition) of HFC-32 in the liquid phase of the refrigerant mixture in the feed vessel to (xy ¹ ) % by weight (minimum value) to (xa) % by weight (maximum value), so that the proportion of HFC-32 in the liquid phase of the refrigerant mixture in the feed container falls within a range of ±a % by weight of a target composition (x) of HFC-32 during the transfer start and end, where ±a is a set tolerance (a > 0); x is an objective composition with the condition that 10 < x < 90, which excludes an interval that satisfies y ¹ >a; yy ¹ is a lower bound on a difference between the target composition and the initial composition, and is represented by Equation (1): lOOOyi = Lix3 - Mix2 Nxx - Pi ( 1) , where L1 = ^0.0002a 0.016, M1 = 0.072a ^3.4761 , N1 = 7.914a ^187.52 and P1 = ^1194.8a - 9.58. 2. A method for filling a refrigerant mixture composed of difluoromethane (HFC-32) and 2,3,3,3-tetrafluoropropene (HFO-1234yf), HFC-32 being present in the liquid phase in an amount of 10-90% by weight based on 100% by weight of total HFC-32 and HFO-1234yf, the method comprising, by transferring the refrigerant mixture in a liquid state to a target container or equipment from a feed container that is filled with the refrigerant mixture in an amount of < 70% by weight of the maximum filling amount of the refrigerant mixture , adjust, immediately before transfer, the proportion (initial composition) of HFC-32 in the liquid phase of the refrigerant mixture in the feed vessel to (xy ² ) % by weight (minimum value) to (xa) % by weight (maximum value), so that the proportion of HFC-32 in the liquid phase of the refrigerant mixture in the feed container falls within a range of ±a % by weight of a target composition (x) of HFC-32 during the transfer start and end, where ±a is a set tolerance (a > 0); x is an objective composition with the condition that 10 < x < 90, which excludes an interval that satisfies y ² >a; yy ² is a lower bound on a difference between the target composition and the initial composition, and is represented by Equation (6): 1000y2 = L2x 3 - M2 ^x 2 N2 ^x - P2 ( 6) , where L ² = -0.0016 to 0.0169, M2 = ^-0.1765 to 3.4316, ^N2 = -1.87 to 180.08 and P2 = ^1119.5 to 148.9. 3. A method for filling a refrigerant mixture composed of difluoromethane (HFC-32) and 2,3,3,3-tetrafluoropropene (HFO-1234yf), HFC-32 being present in the liquid phase in an amount of 10-90% by weight based on 100% by weight of total HFC-32 and HFO-1234yf, the method comprising, by transferring the refrigerant mixture in a liquid state to a target container or equipment from a feed container, adjust, immediately before transfer, the proportion (initial composition) of HFC-32 in the liquid phase of the refrigerant mixture in the feed vessel to (x y3) % by weight (minimum value) to (x a) % by weight (maximum value), so that the proportion of HFC-32 in the liquid phase of the refrigerant mixture in the feed container falls within a range of ±a % by weight of a target composition (x) of HFC-32 during the transfer start and end, where ±a is a set tolerance (a > 0); x is an objective composition with the condition that 10 < x < 90, which excludes an interval satisfying y3 > a; and y3 is a lower bound on a difference between the target composition and the initial composition, and is represented by Equation (11): 1000y3 = L3 ^x 3 - M3 ^x 2 N3 ^x - P3 ( 11) , where L3 = ^0.0003a 0.0172, M3 = 0.0962a ^3.6851 , N3 = ^9.704a 196.9, and ^P3 = 1241.2a - 93.54. 4. The method of any of claims 1-3, wherein 0.5 < a < 3.0. 5. A method for filling a refrigerant mixture composed of difluoromethane (HFC-32) and 2,3,3,3-tetrafluoropropene (HFO-1234yf), HFC-32 being present in the liquid phase in an amount of 10-90% by weight based on 100% by weight of total HFC-32 and HFO-1234yf, the method comprising, by transferring the refrigerant mixture in a liquid state to a target container or equipment from a feed container, adjust, immediately before transfer, the proportion (initial composition) of difluoromethane in the liquid phase of the refrigerant mixture in the feed vessel to (x y4) % by weight (minimum value) to (x 2.0) % by weight ( maximum value), so that the proportion of the difluoromethane in the liquid phase of the refrigerant mixture in the feed vessel falls within a range of ±2.0% by weight of a target composition (x) of the difluoromethane during the start and end of the transfer, where b is an amount (% by weight) initially filled in the feed container; x is a target composition with the condition that 10 < x < 90, which excludes an interval satisfying y4 > 2; and y4 is a lower bound on a difference between the target composition and the initial composition, and is represented by Equation (16): 1000y4 = L4x 3 - M4x 2 ^{N 4 x} - P4 ( 16) , where L4 = 0.0001b ^0.0081 , M4 = ^0.0195b 1.958, N4 = ^0.9878b 118.91, and P4 = ^-0.176b 2408.7. 6. A method for filling a refrigerant mixture composed of difluoromethane (HFC-32) and 2,3,3,3-tetrafluoropropene (HFO-1234yf), HFC-32 being present in the liquid phase in an amount of 10-90% by weight based on 100% by weight of total HFC-32 and HFO-1234yf, the method comprising, by transferring the refrigerant mixture in a liquid state to a target container or equipment from a feed container, adjust, immediately before transfer, the proportion (initial composition) of the difluoromethane in the liquid phase of the refrigerant mixture in the feed vessel to (x y5) % by weight (minimum value) to (x 1.5) % by weight ( maximum value), so that the proportion of the difluoromethane in the liquid phase of the refrigerant mixture in the feed vessel falls within a range of ±1.5% by weight of a target composition (x) of the difluoromethane during the start and end of the transfer, where b is an amount (% by weight) initially filled in the feed container; x is a target composition with the condition that 10 < x < 90, which excludes an interval that satisfies ys > 1.5; and ys is a lower bound on a difference between the target composition and the initial composition, and is represented by Equation (22): 1000y5 = L5x3 - M5x2 N5x - P5 ( 22) , where Ls = 0.00005b 0.0092, Ms = 0.0171b 2.1013, Ns = 0.8528b 125.11, and Ps = -2.372b 1972.3. 7. A method for filling a refrigerant mixture composed of difluoromethane (HFC-32) and 2,3,3,3-tetrafluoropropene (HFO-1234yf), HFC-32 being present in the liquid phase in an amount of 10-18.5% by weight or 60-90% by weight based on 100% by weight of total HFC-32 and HFO-1234yf, the method comprising, by transferring the refrigerant mixture in a liquid state to a target container or equipment from a feed container, adjust, immediately before transfer, the proportion (initial composition) of difluoromethane in the liquid phase of the refrigerant mixture in the feed vessel to (x y6) % by weight (minimum value) to (x 1.0) % by weight ( maximum value), so that the proportion of the difluoromethane in the liquid phase of the refrigerant mixture in the feed vessel falls within a range of ±1.0% by weight of a target composition (x) of the difluoromethane during the start and end of the transfer, where b is an amount (% by weight) initially filled in the feed container; x is a target composition with the proviso that 10 < x < 18.5 wt% or 60 < x < 90 wt%, excluding a range satisfying y6 > 1.0; Y y6 is a lower bound on a difference between the target composition and the initial composition, and is represented by Equation (28): 1000y6 = LeX3 - M6X2 N6X - P6 ( 28) , where L6 = 0.00009b 0.0086, M6 = 0.0183b 2.003, N6 = 0.9237b 117.29, and P6 = -1.055b 1292.7.